CA2184999A1 - Method of isolating isobutylene polymer - Google Patents
Method of isolating isobutylene polymerInfo
- Publication number
- CA2184999A1 CA2184999A1 CA002184999A CA2184999A CA2184999A1 CA 2184999 A1 CA2184999 A1 CA 2184999A1 CA 002184999 A CA002184999 A CA 002184999A CA 2184999 A CA2184999 A CA 2184999A CA 2184999 A1 CA2184999 A1 CA 2184999A1
- Authority
- CA
- Canada
- Prior art keywords
- isobutylene polymer
- polymer
- general formula
- group
- catalyst
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F6/00—Post-polymerisation treatments
- C08F6/02—Neutralisation of the polymerisation mass, e.g. killing the catalyst also removal of catalyst residues
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/26—Removing halogen atoms or halogen-containing groups from the molecule
Abstract
An advantageous process for producing an unsaturated telechelic isobutylene polymer wherein the formed polymer is isolated in a nonaqueous system to prevent the occurrence of an effluent containing the solvent dissolved therein. The process comprises: a method of isolating an isobutylene polymer in a nonaqueous cationic polymerization reaction using a catalyst represented by the general formula (I): MXn (wherein M represents a metal atom; n represents an integer of 2 to 6; and Xs represent each independently halogen or a monovalent hydrocarbon group), characterized by conducting catalyst ligand exchange after the polymerization and removing the component containing the atom M of the above formula (I); a method of isolating an isobutylene polymer in a nonaqueous cationic polymerization reaction using a catalyst represented by the above formula (I), characterized by forming a telechelic isobutylene polymer and removing the catalyst by using an adsorbent capable of adsorbing acids; and a method of isolating an isobutylene polymer in a nonaqueous cationic polymerization reaction using a catalyst represented by the above formula (I), characterized by adding a compound represented by the following general formula (II): Q(OR)m, (wherein Q represents a group Ia, IIa, IIIb or IVa metal atom of the Periodic Table; m represents an integer of 1 to 6; and R represents hydrogen or a monovalent organic group, provided when m is 2 or more, mR's may be the same or different from each other) after the polymerization to eliminate the HC1 molecule from the polymer chain end and conduct catalyst ligand exchange to thereby form an unsaturated telechelic isobutylene polymer, and removing the component containing the atom M of the above formula (I).
Description
218~999 SPECIFICATION
PROCESS FOR ISOLATION OF ISOBUTYI,ENE POLY~ER
[ Technical Field ~
The present invention relates to a process for the isolation of an isobutylene polymer after the polymerization reaction and a process f or the ef f icient production of an isobutylene polymer having telechelic unsaturated groups.
[ Background Art ]
Among telechelic polymers, i . e ., polymers having functional groups at a plurality of ends, polymers having vinyl groups at both ends are useful as starting materials for photo-setting resin, ultraviolet-curing resin, electron radiation-curing resin, sealing compound for electronics, adhesive, modifier, coating material, sealing compound for building, etc.
It ls known that a functional group-terminated polymer, e.g., isobutylene polymer having at both ends a chlorine atom connected to tertiary carbon is produced by the inifer method which comprises the cationic polymerization of isobutylene in the presence of 1, 4-bis (~-chloroisopropyl)benzene [hereinafter simply referred to as "p-DCC" ] as an initiator/chain transfer agent and boron trichloride as a catalyst (U.S. Patent No. 4,276,394).
Further, many reports have been made by Kennedy et al . that, when the f oregoing cationic polymerization reaction is carried out in a solvent containing a halogenated hydrocarbon having one or two carbon atoms ( e . g ., methyl chloride, methylene chloride) in the presence of an electron donor, an isobutylene polymer having a small Mw/Mn value as detr~rminr~d by GPC, i.e., uniform molecular weight, can be obtained [J. Macromol. Sci.-Chem., A18 (1), 25 (1982), Polym.
Bull., 20, 413 (1988), ~olym. Bull., 26, 305 (1991), JP-A-1-318014 (The term ~JP-A~ as used herein means an "lln~ min~oa published Japanese patent application ' ) ] .
In these reactions, a Lewis acid such as BCl3, TiCl4 and AlCl3 is used as a polymerization catalyst. The cationic polymerization reaction can be terminated by adding water to the reaction system so that ligands are exchanged between the I,ewis acid and water, and the Lewis acid is dissolved in water. Thus, the Lewis acid can be separated from the polymer solution by separating the water from the reaction system .
However, this process is disadvantageous in that the separation of the aqueous phase from the organic phase are difficult under certain production conditions. Accordingly, a large amount of water and metal salts are mixed in the organic phase, thus reducing the purity of the product.
Further, a halogen-based organic solvent such as methylene chloride is dissolved in the aqueous solution, requiring an e~LL ly elaborate apparatus for the disposal of waste water. With respect to sCl3 having a low boiling point (12.5C), removal by distillation has reported [JP-A-4-20511, 21~999 specification]. However, since BCl3 is extremely expensive among Lewis acids, it is impracticable as an industrial material. The inventors' object is to provide a process for separating a catalyst from a polymer without generating waste water in the cationic polymerization of isobutylene or the like in the presence of a practical Lewis acid.
In the present invention, it is also made possible to effect a ligand exchange reaction of a catalyst represented by the f oregoing general f ormula ( I ) as well as a dehydrochlorination reaction at ends. The inventors have made extensive studies and, s a result, it was made possible to provide a process for the preparation of a telechelic isobutylene polymer having an unsaturated group by a more ef f ective dehydrochlorination reaction .
The term t~ h~l i c polymer" as used herein means a polymer te~minated by the same or dif f erent f unctional groups which can participate in crosslinking at a plurality of ends thereof .
t Disclosure of the Invention ]
The inventors made extensive studies to find out a process for the isolation/purification of an isobutylene polymer requiring no water-rinsing step.
The present invention has the f ollowing constitutions:
218~999 1. A process for the l&olation of an isobutylene polymer which comprises the cationic polymerization reaction in a non-aqueous system in the presence of a catalyst represented by the following yeneral formula (I):
MX" ( I ) wherein M represents a metallic atom; n represents an integer of from 2 to 6; and the plurality of X may be the same or different and each represent a halogen atom or a monovalent hydrocarbon group, characterized in that the process comprises carrying out polymerization, carrying out the ligand exchange reaction of said catalyst, and then removing a component containing M in the general formula ( I ) .
PROCESS FOR ISOLATION OF ISOBUTYI,ENE POLY~ER
[ Technical Field ~
The present invention relates to a process for the isolation of an isobutylene polymer after the polymerization reaction and a process f or the ef f icient production of an isobutylene polymer having telechelic unsaturated groups.
[ Background Art ]
Among telechelic polymers, i . e ., polymers having functional groups at a plurality of ends, polymers having vinyl groups at both ends are useful as starting materials for photo-setting resin, ultraviolet-curing resin, electron radiation-curing resin, sealing compound for electronics, adhesive, modifier, coating material, sealing compound for building, etc.
It ls known that a functional group-terminated polymer, e.g., isobutylene polymer having at both ends a chlorine atom connected to tertiary carbon is produced by the inifer method which comprises the cationic polymerization of isobutylene in the presence of 1, 4-bis (~-chloroisopropyl)benzene [hereinafter simply referred to as "p-DCC" ] as an initiator/chain transfer agent and boron trichloride as a catalyst (U.S. Patent No. 4,276,394).
Further, many reports have been made by Kennedy et al . that, when the f oregoing cationic polymerization reaction is carried out in a solvent containing a halogenated hydrocarbon having one or two carbon atoms ( e . g ., methyl chloride, methylene chloride) in the presence of an electron donor, an isobutylene polymer having a small Mw/Mn value as detr~rminr~d by GPC, i.e., uniform molecular weight, can be obtained [J. Macromol. Sci.-Chem., A18 (1), 25 (1982), Polym.
Bull., 20, 413 (1988), ~olym. Bull., 26, 305 (1991), JP-A-1-318014 (The term ~JP-A~ as used herein means an "lln~ min~oa published Japanese patent application ' ) ] .
In these reactions, a Lewis acid such as BCl3, TiCl4 and AlCl3 is used as a polymerization catalyst. The cationic polymerization reaction can be terminated by adding water to the reaction system so that ligands are exchanged between the I,ewis acid and water, and the Lewis acid is dissolved in water. Thus, the Lewis acid can be separated from the polymer solution by separating the water from the reaction system .
However, this process is disadvantageous in that the separation of the aqueous phase from the organic phase are difficult under certain production conditions. Accordingly, a large amount of water and metal salts are mixed in the organic phase, thus reducing the purity of the product.
Further, a halogen-based organic solvent such as methylene chloride is dissolved in the aqueous solution, requiring an e~LL ly elaborate apparatus for the disposal of waste water. With respect to sCl3 having a low boiling point (12.5C), removal by distillation has reported [JP-A-4-20511, 21~999 specification]. However, since BCl3 is extremely expensive among Lewis acids, it is impracticable as an industrial material. The inventors' object is to provide a process for separating a catalyst from a polymer without generating waste water in the cationic polymerization of isobutylene or the like in the presence of a practical Lewis acid.
In the present invention, it is also made possible to effect a ligand exchange reaction of a catalyst represented by the f oregoing general f ormula ( I ) as well as a dehydrochlorination reaction at ends. The inventors have made extensive studies and, s a result, it was made possible to provide a process for the preparation of a telechelic isobutylene polymer having an unsaturated group by a more ef f ective dehydrochlorination reaction .
The term t~ h~l i c polymer" as used herein means a polymer te~minated by the same or dif f erent f unctional groups which can participate in crosslinking at a plurality of ends thereof .
t Disclosure of the Invention ]
The inventors made extensive studies to find out a process for the isolation/purification of an isobutylene polymer requiring no water-rinsing step.
The present invention has the f ollowing constitutions:
218~999 1. A process for the l&olation of an isobutylene polymer which comprises the cationic polymerization reaction in a non-aqueous system in the presence of a catalyst represented by the following yeneral formula (I):
MX" ( I ) wherein M represents a metallic atom; n represents an integer of from 2 to 6; and the plurality of X may be the same or different and each represent a halogen atom or a monovalent hydrocarbon group, characterized in that the process comprises carrying out polymerization, carrying out the ligand exchange reaction of said catalyst, and then removing a component containing M in the general formula ( I ) .
2. The process for the Lsolation of an isobutylene polymer according to the f oregoing paragraph 1, wherein said ligand exchange reaction is effected with the addition of a compound represented by the following general formula (II):
Q(OR)= (II) wherein Q represents a metallic atom belonging to the group I,, II,, III~, or IV" of the periodic table; m represents an integer of from 1 to 6; and R represents a hydrogen atom or a monovalent organic group, with the proviso that when m is 2 or more, the plurality of R may be the same or different, and Rimultaneously producing a telechelic isobutylene polymer.
Q(OR)= (II) wherein Q represents a metallic atom belonging to the group I,, II,, III~, or IV" of the periodic table; m represents an integer of from 1 to 6; and R represents a hydrogen atom or a monovalent organic group, with the proviso that when m is 2 or more, the plurality of R may be the same or different, and Rimultaneously producing a telechelic isobutylene polymer.
3 . A process f or the isolation of an isobutylene polymer which comprises the cationic polymerization in a non-aqueous system in the presence of a catalyst represented by the foregoing general formula (I), characterized in that the process comprises producing a telechelic isobutylene polymer and simultaneously removing said catalyst with an adsorption material capable of adsorbing an acid.
4. A process for the isolation of an isobutylene polymer, which comprises carrying out cationic polymerization reaction in a non-aqueous system in the presence of a catalyst represented by the foregoing general formula (I);
adding a compound represented by the f oregoing qeneral formula (II) to effect the dehydrochlorination reaction at the ends of the polymer and the ligand exchange reaction of the catalyst so as to produce a telechelic isobutylene polymer having an unsaturated group; and removing a component containing M in the general f ormula ( I ) .
adding a compound represented by the f oregoing qeneral formula (II) to effect the dehydrochlorination reaction at the ends of the polymer and the ligand exchange reaction of the catalyst so as to produce a telechelic isobutylene polymer having an unsaturated group; and removing a component containing M in the general f ormula ( I ) .
5. The process for the isolation of an isobutylene polymer according to the foregoing paragraph 2 or 4, wherein said compound represented by the general formula (II) comprises at least one compound or a plurality of ~ ullds selected from the group consisting of NaOH, ROH, LiOH, Ca(OH)2, NaHCO3, NaOCH3, ~OCH3, LiOCH3, Ca(OCH3)2, Ng(OCH3)2, Al ( OCH3 ) 3, Ti ( OCH3 ) 4, NaOCH2CH3, ~OCH2CH3, IJiOCH2CH3, Ca ( OCH2CH3 ) 2, Ng ( OCH2CH3 ) 2, Al ( OCH2CH3 ) 3, Ti ( OCH2CH3 ) 4, NaOC ( CH3 ) 3, KOC ( CH3 ) 3, LiOC ( CH3 ) 3, NaOC ( CH3 ) 2CH2CH3, and Al[OCH(CH3)2]3 -6. The process for the isolation of an isobutylene polymer according to the foregoing paragraph 4 or 5, wherein 6aid dehydrochlorination at the ends of the polymer is effected under reduced pressure, i.e., not higher than 700 mmHg .
7. The process for the isolation of an isobutylene polymer according to any one of the foregoing paragraphs 1, 3, 5 and 6, wherein the f ollowing components ( 1 ) to ( 5 ) were mixed at a temperature of from -100C to 0C to prepare an isobutylene polymer:
( 1 ) a cationically poly - 7~hle monomer having isobutylene;
( 2 ) a compound represented by the f ollowing general formula (III):
~3 ( I I I ) wherein Rl represents an aromatic ring group or substituted or unxubstituted aliphatic hydrocarbon group; R2 and R3 may be the same or different and each represent a hydrogen atom or substituted or unsubstituted monovalent hydrocarbon group, with the prQViso that when Rl is an aliphatic hydrocarbon group, at least one of R2 and R3 is not a hydrogen atom; X
reprexents a halogen atom, R4Coo- group (in which R4 reprexents a hydrogen atom or a Cl 5 alkyl group) or R50-group (in which R5 l~:ul~su-lLs a llyd- U~l atom or a Cl 5 alkyl group ); and w represents an integer of f rom 1 to 8;
(3) a catalyst represented by the foregoing general formula (I);
( 4 ) an electron donor component having a donor number of from 15 to 50; and ( 5 ) a reaction solvent .
In general, when the ligand exchange reaction is effected in the presence of a compound represented by the foregoing general formula ( II ), a small amount of a compound represented by the general formula GOH [in which G represents a llydlvy~ll atom or a monovalent hydrocarbon group ] can be used as a catalyst. For example, CH30H, CH3CH20H, (CH3)2CHOH, a slight amount of water, etc. may be used.
The term "non-aqueous system" as used herein does not necessarily mean a system which employs no water but means a system which generates no waste water. If necessary, an extremely small amount of water may be added to cause the ligand exchange reaction of the catalyst to proceed smoothly.
In such a case, the water thus added is adsorbed by the adsorbing material capable of adsorbing an acid in the reaction solution, thus generating no waste water.
In the present invention, the isobutylene polymer normally has a number-average molecular weight (Mn) of from 500 to 300,000, preferably from 1,000 to 50,000. If ~n is less than 500, the excellent characteristics inherent to isobutylene polymer are lost. On the contrary, if Mn exceeds 300,000, the resulting polymer is solid, extremely 2i84999 deteriorating the workability thereof. The number-average molecular weight (Mn) and Mw/Mn value of the isobutylene polymer were determined by GPC using a polystyrene gel column [Shodex K-804, available from Showa Denko R.E~.; mobile phase:
chloroform] as a polystyrene-based value.
As the catalyst component represented by the foregoing general formula (I) for the present invention, any metallic complex known as Lewis acid may be used without any restriction. In general, TiC14, SnCl4, AlC13, CH3CX2AlC12, (CH3CH2)2AlCl, VCl5, FeCl3, BF3, etc. may be used. However, the catalyst ~ t is not limited to these compounds.
Among these Lewis acids, TiCl4, SnCl4, and AlCl3 are pref erable .
In the present invention, the Lewis acid is normally used in an amount of from 0.1 to 10096 by weight, preferably from 1 to 309~ by weight based on the weight of the cationically poly 7~hle monomer having isobutylene. If the amount of the Lewis acld to be used as a catalyst component is less than 0.196 by weight, the yield of the cationic polymerization reaction decreases. On the contrary, if the amount of the Lewis acid to be used exceeds 10096 by weight, no f urther merits can be obtained .
As the compound represented by the f oregoing general formula (II) for the present invention, any ~ d containing a metallic atom belonging to the group I., II~, IIIb or IV" of the periodic table may be used without any restriction. In general, NaOH, ROH, LiOH, Ca(OH)2, NaHCO3, NaOCH3, KOCH3, LiOCH3, Ca ( OCH3 ) 2, Mg ( OCH3 ) z, Al ( OCH3 ) 3, Ti ( OCH3 ) 4, NaOCH2CH3, KOCH2CH3, LiOCH2CH3, Ca ( OCH2CH3 ) 2 r Mg ( OCH2CH3 ) 2, Al ( OCH2CH3 ) 3, Ti ( OCH2CH3 ) 4, NaOC ( CH3 ) 3, ROC ( CH3 ) 3, LiOC(CH3)3, NaOC(CH3)2CH2CH3, Al[OCH(CH3)2]3, etc. may be used.
Among these compounds, NaOC~3, KOCH3, NaOH, KOH, and NaOCHzCH3 are pref erable .
In the present invention, the compound represented by the general formula ( II ) is normally used in an amount of from 0.1 to 100 mol, preferably from 2 to 20 mol per 1 mol of the catalyst component represented by the foregoing general formula (I). If the amount of the compound represented by the general formula (II) to be used is less than 0.1 mol per mol of the catalyst component, the separation of the polymer from the catalyst is difficult. On the contrary, if the amount of the compound represented by the general f ormula ( II ) to be used exceeds 100 equivalents, no further merits can be obtained.
In the present invention, the ligand exchange reaction is normally effected under normal pressure or reduced pressure at a temperature of from -100C to 150C for 1 to 600 minutes. In the present invention, the removal of the Lewis acid catalyst after the ligand exchange can be a- ~ li fih~d by filtration, if the metallic complex derived from the catalyst is solid, or by distillation under reduced pressure, if the metallic complex derived from the catalyst _ 9 _ is liquid. However, the present invention is not limited to these methods, and any methods are practicable.
In the present invention, as the adsorbing material capable of adsorbing an acid for use in the removal of the catalyst, compounds mainly composed of at least one of ~-activated carbon, titanium oxidej Mg, Al and/or Si may be used. E:xamples of such a compound containing Si include aluminum silicate ( silica alumina ), molecular sieves (zeolite), silica gel, alumina gel, and activated clay.
Among these adsorbing materials, activated carbon and aluminum silicate are preferable.
In the present invention, the adsorbing material capable of adsorbing an acid is normally used in an amount of from 0.2 to 300 times, preferably from 3 to lO0 times the weight of the compound represented by the f oregoing general f ormula ( I ) . The temperature at which adsorption is ef f ected is normally from -100C to 40C, preferably from -70C to 25C. The reaction time is normally from I second to 10 hours .
In the present invention, the cationically polymerizable monomer containing isobutylene is not limited to a monomer made of isobutylene alone. The cationically poly 7~hle monomer containing isobutylene of the present invention contains a monomer copoly 7Ahle with isobutylene, preferably in an amount of not more than 5096 by weight (hereinafter simply referred to as "96 ' ) .
_ 10 --, .
Examples of the cationically polymerizable monomer copolymerizable with isobutylene include C3 l2 olefins, con~ugated dienes, vinyl ethers, aromatic vinyl compounds, norbornenes, and vinyl silanes. Amony these cationically poly 7;lhle r~n~ ~ C3 lz olefins and aromatic vinyl compounds are pref erable .
Specific examples of the cationically polymerizable monomer copolymerizable with isobutylene usually include propene, 1-butene, 2-butene, 2-methyl-1-butene, 3-methyl-1-butene, pentene, hexene, cyclohexene, vinylcyclohexane, 5-ethylidenenorbornene, 5-propylidenenorbornene, butadiene, isoprene, cyclopentadiene, methyl vinyl ether, ethyl vinyl ether, isobutyl vinyl ether, vinyl carbazole, methu.~y~LyLe-~e, ethu~y~l~y~ e~ t-butu~y~l yL~IIe~ hexenyloxy styrene, styrene, a-methylstyrene, methylstyrene, dimethylstyrene, chloromethylstyrene, chlorostyrene, indene, ,~-pinene, vinyltrichlorosilane, vinylmethyldichlorosilane, vinyldimethylchlorosilane, vinyldimethylmethoxysi1ane, vinyltrimethylsilane, divinyldichlorosilane, divinyldimethoxysilane, divinyldimethylsilane, 1,3-divinyl-1,1, 3, 3-tetramethyldisiloxane, trivinylmethylsilane, y-methacryloylu~y~Lu~yltrimethoxysilane~ and y-methacryloylu~y~Lu~ylmethyldimethoxysilane .
Among these cationically poly z~hle - I s, propene, l-butene, 2-butene, cyclopentadiene, 5-ethylidene norbornene, isobutyl vinyl ether, methoxystyrene, and styrene and the like are preferable. One of these cationically poly -~ 7Ahle monomers copolymerizable with isobutylene may be used in combination with isobutylene, and two or more of these cationically poly 7Ahle monomers may be used in combination .
In the present invention, the concentration of the cationically poly - - 7Ahle monomer containing isobutylene in the batch process is normally from 0.1 to 10 mol/Q, preferably from 0.5 to 6 mol/Q.
Examples of the compound represented by the f oregoing general formula (III) of the present invention include a compound represented by the following general formula (IV):
AY, ( IV ) wherein A represents a group having l to 4 aromatic rings, n represents an integer of from l to 8, and Y represents a group represented by the following general formula (V):
lR6 wherein R6 and R7 may be the same or dif f erent and each represent a hydrogen atom or a Cl 20 monovalent hydrocarbon group, and X represents a halogen atom, a R4Coo- group (in which R4 represents a hydrogen atom or Cl 5 alkyl group) or a R50- group (in which R5 represents a hydrogen atom or a Cl 5 alkyl group); a compound represented by the following general formula (VI ):
BZD, (VI ) wherein B represents a C4 40 substituted or unsubstltuted hydrocarbon group, Z represents a halogen atom connected to the tertiary carbon atom, a R8C00- group (in which R8 represents a hydrogen atom or a Cl 5 alkyl group) or a R90-group (in which R9 represents a' hydrogen atom or a Cl 5 alkyl group ), and m represents an integer of f rom 1 to 4 ; and an oligomer having cL-halostyrene units, but are not limited to these compounds. These compounds may be used alone or in combination of two or more.
In the compound represented by the general formula ( IV), the group having 1 to 4 aromatic rings represented by A
may be produced by conllPn~tion reaction or may not be a condensation product. Examples of the group containing aromatic rings include groups having a valence of ~rom 1 to 6 which is derived from benzene, biphenyl, naphthalene, anthracene, phenanthrene, pyrene, Ph- ( CEI2 ) l-Ph ( in which Ph represents a phenyl group, and 1 represents an integer of from 1 to 10 ) . These groups having aromatic rings may be substituted by Cl 20 straight and/or branched aliphatic hydrocarbon groups or groups containing a functional group such as a hydroxyl group, an ether group and a vinyl group.
As the compound represented by the general formula (VI ), compounds having a functional group other than z, such as vinyl group and silyl group, may be used.
218~999 Examples of the oligomer having c~-halostyrene units which can be used as the initiator/chain transfer agent include oligomer of ~-chlorostyrene, and oligomer obtained by the copolymerization of ~-chlorostyrene with a monomer copolymerizable with styrene.
In the present invention, it is advantageous to use, among the compounds represented by the general formula (III), a compound having two or more of halogen atoms, R4Coo- groups (in which R4 represents a hydrogen atom or a Cl 5 alkyl group) or R50- groups ( in which R5 represents a hydrogen atom or a Cl 5 alkyl group) or a compound having a halogen atom, a R4Coo- group or a R50- group together with reactive functional groups as an initiator/chain transfer agent since the resulting polymer has a higher functionality.
Specif ic examples of the compound represented by the foregoing general formula (III) which can be normally employed include the following compounds:
X--C~ ICH - 3X X--C~ C(CH333 CX(CH3)2 Cx(cH3)2 X--C ~ CH~ Cl H - X
CH3 CX(CH3)2 CH3 CH3 218~999 CH3~C--X X--C~CH2CH2~ IH - 3X
CH3 CHl CH3 CHJ
X--C~CH2CH2CH2 ~ ICH - X
CH3 CH3 Cl H3 (n-c8H17) (n-c8H17) CH3 CH3 ICH3 X--c--CH2CH2CH2CH2--C--X X--C--CH2CH2--C--CH2CH2--C--X
(n-CsH17) (n-CsH17) CH
H2C=CH-CH2CH2CH2CH2-- ~ CH2--X H2C=CH-CH2CH2CH2CH2--C--X
H
H2C=CH-CH2CH2CH2CH2-- ~ C--X
wherein X represents a halogen atom, a R4Coo- group ( in which R4 represents a hydrogen atom or a C1 5 alkyl group) or a R50-group (in which R5 represents a hydrogen atom or Cl 5 alkyl group), and oligomer of ~-chlorostyrene, but are not limited to these compounds . Among these compounds, pref erable ones are:
218~999 .
Cl--C~ C--Cl Br--C ~ C--~r CH3 Ccl(cH3)2 CH3 C(CH3)3 Cl-C~ Cl-C~
CH3 Ccl(cH3)2 CCI(CH3)2 Cl C ~ CH2CH2 ~ C--Cl Cl--C ~ CH2cH2cH2 ~g~ l H - Cl Cl--C--C--Cl CH3 CH3 . CH3 CH3 Cl--C--CH2CH2--C--CH2CH2--C--Cl Hzc=cH-cH2cH2cH2cH2--O~CH2--Cl H2c=cH-cH2cH2cH2cH2--C--Cl H
H2c=cH-cH2cH2cH2cH2-- ~ C--Cl -- 218~999 C~3COO- group-containing compounds such as O
o CH3 CH3 I CH3 0 CH3 C=O CH3 CH3~0 --C~C--OCCH3 CH3l~0--C~C(CHI)2 O~CH
C(CH3)2 o CCH
and C~I30- group-containing compounds such as CHl CH3 CH3 CH3 rCH3 CH30--C--CH2--O--CH2--C--OCH3 CH30--C ~ C--OCH3 CH~ ( 2 3 CH3 C(CHI320CH3 These compounds are components which are used as initiators/chain transfer agents. These cl ~ u-Lds may be ~ 2184999 used alone or as a mixture of two or more in the present invention. By controlling the amount of these compounds to be used, the number-average molecular weight of the resulting isobutylene polymer can be arbitrarily predetF~nni n~d.
In the present invention, the amount of the compound represented by the foregoing general formula (III) to be used is normally from 0.01 to 20~ by weight, preferably from 0.1 to 10% by weight based on the weight of the cationically polymerizable monomer containing isobutylene.
As the electron donor component f or the present invention, any known electron donor components having a donor number of from 15 to 50 may be used. Preferred examples of such electron donor components include pyridines, amines, amides, and sulfoxides, but are not limited to these compounds .
Specific examples of the electron donor component for the present invention include 2,6-di-t-butylpyridine, 2-t-butylpyridine, 2, 4, 6-trimethylpyridine, 2, 6-dimethylpyridine, 2-methylpyridine, pyridine, diethy1amine, trimethylamine, triethylamine, tributylamine, diethylamine, N,N-dimethylaniline, N,N-dimethylformamide, N, N-dimethylacetamide, N, N-diethylacetamide, dimethylsulfoxide, diethyl ether, methyl acetate, ethyl acetate, trimethyl phosphate, and hexamethylphosphoric triamide. Among these electron donor ~ n~ntS, 2,6-di-t-butylpyridine, 2, 6-dimethylpyridine, 2-methylpyridine, 218~999 pyridine, diethylamine, trimethylamine, triethylamine, N,N-dimethylformamide, N,N-dimethylacetamide, and dimethylsulfoxide are preferable. Picolines are further pref erred . Among these electron donors, 2-methylpyridine is particularly preferred since a L` rk~hle effect can be obtained even with its small donor number.
In the present invention, the electron donor component is normally used in an amount of from O . 01 to 10 mol, preferably from 0.1 to 2 mol per mol of the compound represented by the general formula (III).
As the reaction solvent for the present invention, halogenated hydrocarbons, aliphatic hydrocarbons, aromatic hydrocarbons or the like may be used. Examples of the halogenated hydrocarbon include methyl chloride, methylene chloride, 1, l-dichloroethane, 1, 2-dichloroethane, 1-chloropropane, 1-chloro-2-methylpropane, 1-chlorobutane, l-chloro-2-methylbutane, l-chloropentane, l-chlorohexane, and l-chloro-2-methylhexane. Examples of the aliphatic or aromatic hydrocarbon include butane, pentane, neopentane, hexane, cyclohexane, methylcyclohexane, heptane, octane, benzene, toluene, and xylene.
Examples of the mixed solvent which can be used in the pre6ent invention include various combinations such as methylene chloride/hexane, 1, 2-dichloroethane/hexane, l-chlo~opLu~d~le/hexane, l-chlorobutane/hexane and 1 -chloropentane/hexane .
~ 218~999 In the present invention, the polymerization reaction is not specif ically limited and can be carried out by any conventional polymerization method. Among the foregoing components, i . e ., ( 1 ) a cationically polymerizable monomer having isobutylene, (2) a compound represented by the general formula (III), (4) a Lewis acid, and (5) an electron donor component, a solution containing (4) a Lewis acid may be added to a solution containing a cationically poly - 7~hle monomer containing lsobutylene in a batch process.
Alternatively, a solution containing ( 1 ) a cationically poly ri 7~hle monomer containing isobutylene may be continuously added to a solution containing ( 4 ) a Lewis acid in a semi-batch process. Further, a continuous process may be employed in which all the foregoing components are continuously charged into the reaction system while removing the reaction product.
In the present invention, if the ligand exchange reaction of the catalyst represen~ed by the foregoing general formula ( I ) is accompanied by the dehydrochlorination reaction at the ends of the polymer, any compounds represented by the foregoing general fo~mula ( II ) may be used without any restriction. Preferred examples of such a ~ u~ld include NaOH, ROH, LiOH, Ca(OH)2, NaHCO3, NaOCH3, ~OCH3, LiOCH3, Ca ( OCH3 ) z, NaOCH2CH3, ROCH2CH3, LiOCH2CH3, NaOC ( CH3 ) 3, ROC ( CH3 ) 3, 1: iOC ( CH3 ) 3, NaOC ( CH3 ) zCHzCH3, and Al[OCH(CH3)2]3 -218~999 In the present invention, if the ligand exchange reaction of the catalyst represented by the foregolng general formula (I) is accompanied by the dehydrochlorination reaction at ~he ends of the polymer, the dehydrochlorination reaction is preferably effected under reduced pressure. The dehydrochlorination reaction is normally ef f ected under a pressure of not higher than 700 mmHg, preferably not higher than 20 ml~3Hg, and more preferably not higher than 1 mmHg. A
process for the preparation of an isobutylene polymer having telechelic unsaturated groups in the presence of NaOC~3, ~OC(CH3)3 or the like under normal pressure has already been known. However, the reaction under normal pressure is disadvantageous in that the reaction rate is actually low.
In particular, it takes from 20 to 30 hours to complete the reaction at temperatures of not higher than 100C [see examples described in U.S. Patent No. 4,316,973 and JP-A-1-261405]. Then, the inventors made extensive studies and, as a result, it was f ound that the dehydrochlorination reaction can be accelerated by reducing the pressure of the reaction system. The dehydrochlorination reaction at the ends of the polymer is considered to be an E2 reaction from the st~n~lr~int of reaction mechanism. Further, this elimination reaction is considered to be an irreversible reaction. Thus, it hardly can be considered in common sense that this reaction can be accelerated under reduced pressure.
Accordingly, it can be said that an unexpected effect appeared. The reaction temperature at which the dehydrochlorination reaction occurs is normally from 30C to 300C, preferably from 60C to 200C. If possible, the reaction is preferably effected~ with stirring without solvent .
[Best Mode for Carrying out the Invention]
The present invention will be further described in the following examples, but the present invention should not be construed as being limited thereto.
Structural analysis of isobutylene polymer The structure of the isobutylene polymer obtained in the examples was determined by IH-NMR spectrometry and GPC
analysis. The measuring instruments used and the conditions for mea~ul~ ts will be given below.
H-NMR spec~rometry (300 MHz): Gemini-300, available from Varian Corp. (measured in a mixture of heavy acetone and carbon tetrachloride ) GPC analysis: System: System available from Waters Corp. (Pump 600E, Differential Refractometer 401, etc. ) Column: Shodex-804 (polystyrene gel), available from Showa Denko K.~t.
~ 2184999 Mobile phase: chloroform (number-average molecular weight, etc. are de~rmi n~d as a polystyrene-based value ) The air in a 200 mQ-capacity pressure-resistant glass vessel equipped with a magnetic stirrer and a three-way cock was replaced by nitrogen. Into the vessel were charged 5g mQ
of methylene chloride (which had been allowed to stand overnight or longer with molecular sieves 3A for drying), 37 mQ of hexane (which had been allowed to stand overnight or longer with molecular sieves 3A for drying), and 0.139 g (0.6 mmol) of 1,4-bis(c~-chloroisopropyl)benzene [p-DCC]
through a syringe. Then, a pressure-resistant liquefied gas-collecting glass tube equipped with a needle valve in which 8 mQ (96 mmol) of iso~utylene monomer had been charged was connected to the three-way cock. The polymeri2ation vessel was then dipped in a -70C dry ice/ethanol bath for cooling.
The air was then evacuated from the vessel by a vacuum pump.
The needle valve was then opened so that the isobutylene monomer was introduced from the liquefied gas-collecting tube into the polymerization vessel. Nitrogen gas was then introduced into the polymerization vessel from one of the three ways of the cock so that the pressure of the vessel was returned to normal value. A methylene chloride solution (1 ml containing 11.2 uQ (0.12 mmol) of 2-methylpyridine was ~ 218~999 added into the polymerization vessel, and stirring of the monomer solution was then started at a temperature of -70C.
A methylene chloride 801utLon ( 3 me ) containing 0.33 me (3 mmol) of titanium tetrachloride was then added to the polymerization solution through a syringe to initiate cationic polymerization reaction. The polymerization solution was allowed to undergo cationic polymerization reaction at a temperature of -70C for 60 minutes.
Thereafter, 5.8 g of a methanol solution of 1.62 g (30 mmol) of sodium methoxide (sodium methoxide content: 28%) was added to the polymerization solution at -70C. The polymerization vessel was withdrawn from the dry ice/ethanol bath, and then dipped in a hot water bath so that the temperature of the polymer solution was raised to 40C. The polymer solution was then moved into a 300 me-capacity eggplant-type f lask . The volatile content was then removed at a temperature of 100C under reduced pressure (not higher than 1 mm~Ig ) by means of an evaporator in 2 hours . EIexane (200 me) was then charged into the eggplant-type flask to dissolve the isobutylene polymer. The solution was then filtered through a Kiriyama funnel filter paper (No. 4;
retained particle: 1 llm) with suction. The volatile content was then evaporated to obtain 6.1 g of a colorless transparent isobutylene polymer. The properties of the polymer thus ob~ained are shown in Table 1.
Ti and Na, which are considered to be contaminating the polymer, were then determined. The results of the analysis are also shown in Table 1.
Into a le-capacity separable flask equipped with a mechanical stirrer and a three-way cock was charged 1. 65 g ( 7 .14 mmol ) of p-DCC. The air in the vessel was then replaced by nitrogen, and 83 mQ of methylene chloride (which had been allowed to stand overnight or longer with molecular sieves 3A for drying) and 174 mQ of hexane (which had been allowed to stand with molecular sieves 3A overnight or longer for drying) were then added to the polymerization system through a syringe.
To the three-way cock was then connected a liquefied gas-collecting pressure-resistant glass tube equipped with a needle valve in which 85.5 mQ of isobutylene monomer had been charged. The polymerization vessel was then dipped in a -75 C dry ice/ethanol bath f or cooling . The air was then evacuated from the vessel by a vacuum pump. The needle valve was then opened so that the isobutylene monomer was introduced from the liquefied gas-collecting tube into the polymerization vessel. Nitrogen gas was then introduced into the polymerization vessel from one of the three ways of the cock so that the pressure of the vessel was returned to normal value. A solution obtained by diluting O.133 g (1.43 mmol) of rY-picoline [2-methypyridine] with 1 mQ of methylene chloride was then added into the polymerization vessel. The monomer solution was then stirred at a temperature of -75CC by means of a mechanical stirrer. ~ --~
A solution obtained by diluting 1.04 m~ (9.52 mmol) of titanium tetrachloride with 12 mQ of methylene chloride was then added into the polymerization vessel. The polymerization system was then allowed to undergo polymerization reaction at a temperature of -75C for 60 minutes. Thereafter, 8.5 mQ (114 mmol) of methanol and 5.39 g (100.0 mmol) of sodium methoxide were added to the polyisobutylene (PIB) solution at -75C, followed by stirring. The polymerization vessel was withdrawn from the dry ice/ethanol bath, and then dipped in a hot water bath so that the temperature of PIB solution was raised to about 4o C .
The vessel was then dipped in a 50C oil bath. The volatile content was evaporated under normal pressure and under reduced pressure while the temperature of the system was being gradually raised to 100C. The mixture of PIB and a white powder which had Ll ;notl in the vessel was then stirred for 60 minutes by means of the mechanical stLrrer under reduced pressure ~not higher than 1 mmHg, evacuated by a vacuum pump) while the system was being heated to a temperature of 100C. IIexane (500 mQ) was then added into the vessel to dissolve PIB. The solution was filtered through a Kiriyama f ilter paper to recover a solid content .
218~999 Hexane was then evaporated to obtain 57 . 4 g of an isu~Lu~ yl-terminated PIB. The properties of the polymer thus obtained are shown in Table 1.
Table l GPC 96, Proportion ElementarY analYsis r96) of isu~luy~
Mn Mw/Mn groupl) at end Ti2) Na3) Example l 11300 1.22 gl c 0.001 c 0.001 Example 2 8800 1. 37 94 -- -- =
1 ) Isopropenyl group: -CX2C ( CH3 ) =CH2 2) The sample was wet-decomposed, and then detprminl~d by ICP
emission spectroscopic analysis.
3) The sample was dry-decomposed, and then det~rmin--fl by atomic absorption spectroscopy.
The resuLts set forth in Table 1 show that the isobutylene polymers obtained in Examples 1 and ~ contain little or no Ti or ~a. Thus, it is clear that high purity polymers containing little or no impurities were obtained.
Table 1 also shows that the processes of Examples 1 and 2 are processes for the effective preparation of an isopropenyl-terminated isobutylene polymer.
[PrF~l iminAry Examination 1] Measurement of water absorption of metal oxide Titanium oxide ( 1. 00 g) (available from Wako Pure Chemicals Co., Ltd. ) was weighed in a ground glass Erlenmeyer flask which had been thoroughly dried. Then, 91.6 g (100 mQ) of a 4/6 (by volume) mixture of methylene chloride and n-hexane and a predetermined amount of water were added, and the reaction mixture was then stirred at room temperature for I hour. The resulting slurry was then filtered through a No.
4 Kiriyama filter paper with suction. Free water in the f iltrate was then measured by the Karl Fischer moisture meter .
The water content in the air, the water content which had previously been adsorbed by titanium oxide and the water content in the mixed solvent were determined by blank test.
The water content in the filtrate was then de~ nl~d by subtracting these water contents f rom measured value . The results are shown in Takle 2. It was found that when the weight of the water content adsorbed by titanium oxide is up to 1. 5 times greater than that of titanium oxide, the filtrate is not separated into two phases.
[ Preparation Example 1 ] Preparation of polymer solution ( l ) A pressure-resistant vessel equipped with a mechanical stirrer was thoroughly dried, and the air in the vessel was thoroughly replaced by nitrogen. Into the vessel were then charged 112 mQ of methylene chloride which had been previously dehydrated through molecular sieves 3A, 173 mQ of n-hexane, 0 . 289 g of p-DCC and 0 . 047 g of ~-picoline . The vessel was then cooled to a temperature of -70C, 28 mQ of an isobutylene monomer was then transferred to the vessel.
'~ 21'84~g9 Then, 6.83 g (36 mmol) of titanium tetrachloride was added through a dried syringe while nitrogen was being introduced at a small rate through a three-way cock so as to initiate polymerization. The polymerization system was stirred at the same temperature for 1 hour. To the polymerization system was then added 9.96 g of 1,9-decadiene. The polymerization system was further stirred for 4 hours to introduce a carbon-carbon double bond into the ends of the polyisobutylene. The polymer solution obtained in the present Preparation Example will be hereinafter referred to as "polymer solution l".
EXA~PLE 3 Into an eggplant-type flask was charged 32.4 mQ
(159 mmol) of a 4.90 N methanol solution of sodium methoxide.
The polymer solution 1 at a temperature of -70C was then slowly poured into the polymerization sy~tem. The polymerization system was then stirred until the temperature of the content was returned to room temperature, i.e., for 30 minutes. The flask was then dipped in a 100C oil bath, the solvent was then evaporated under reduced pressure. After 15 minutes, the f lask was removed the evaporator . The content of the flask was then washed with 50 mQ of n-hexane twice to dissolve the polymer therein. The slurry containing a polymer solution was then filtered through a No. 4 ~iriyama filter paper with suction. The resulting transparent filtrate was heated over a 130C oil bath under reduced pressure for 1 hour to isolate 18 . 8 g of a polymer.
The GPC and NMR analysis of the polyisobutylene obtained are shown in Table 3. The results of atomic absorption spectroscopy o~ sodium and ICP analysis of titanium in the polymer are also shown in Table 3.
EXA~P1E 4 Into a flask were charged 11.78 g (159 mmol) of calcium hydroxide and 3 . 0 g of water. The polymer solution 1 at a temperature of -70C was then poured into the polymerization system. The polymerization system was then stirred at room temperature f or 3 hours . The resulting slurry content was then filtered through a No. 4 filter paper with suction. To the resulting filtrate was then added 1 g of aluminum silicate. The mixture was then stirred at room temperature f or 3 hours, and then f iltered through a No . 4 ~iriyama filter paper with suction. The filtrate was then sub~ected to evaporation under reduced pressure in the same manner as in Example 3 to isolate a polymer. The polymer thus obtained will be hereinafter referred to as ~polymer 2".
The results of GPC and Nr~R analysis of the polymer 2 are shown in Table 4 with the results of determination of sodium and titanium in the polymer 2.
EXA~PI.E 5 In the same manner as in Example 4 except that 8.59 g of a sodium methoxide powder was used instead of calcium hydroxide, a polymer was lsolated. The results are shown in Table 4.
2184~
In the same manner as in Example 4 except that 13 . 36 g of a sodium hydrogencarbonate powder was used instead of calcium hydroxide, a polymer was isolated. The results are shown in Table 4.
COMPAR~TIVE E~AMPLE 1 The polymer solution 1 at a temperature of -70C was poured into 300 m~ of water to inactivate a catalyst. The aqueous phase was then removed by decantation, and the inin~ organic phase was then repeatedly washed with 300 me of ion-exchanged water until the electrical conductance of the waste water reached constant. For this purpose, washing was needed three times. As a result, 1, 200 m~ of waste water containing methylene chloride and n-hexane in a saturated concentration was generated.
The waste water was then subjected to evaporated under reduced pressure in the same manner as in Example 3 to isolate a polymer. The results of analysis of the polymer are shown in Table 5.
The polymer solution 1 was heated in a 45C bath to evaporate methylene chloride. The generation of hydrogen chloride was recognized during heating. Thus, a serious corrosion occurred in the gas phase area of a metallic vessel (material: SUS316L). When the distillation was stopped, the .
21849~9 content of the vessel was poured into 300 m~ of water, and washing with water was repeated three times.
The material was then subjected to evaporation under reduced pressure in the same manner as in Example 3 to isolate a polymer. The results of analysis are shown in Table 6.
Table 2: Water absorption of metal oxide Titanium Amount of Water/titanium Water content Filtrate oxide water added oxide ratio in f iltrate Condition (mg) (mg) (mol/mol) (ppm) 984.1 505.9 2.28 225 994 . 0 756 . 0 3 . 38 226 994.0 1006.0 4.4g 244 994.0 1506.0 6.72 214 991.5 2008.5 8.99 355 +
991.5 2508.5 11.23 435 +
1051 . 0 3009 . 0 12. 71 441 +
1011.3 4008.7 17.59 448 +
994 . 0 5006 . 0 22 . 35 415 +
1001.4 7008.6 31.07 451 +
Note) --: The filtrate was uniform.
+: The f iltrate was separated into two phases: aqueous phase and organic phase.
218~999 Table 3 Mn Mw/Nn Fn(v) Sodium i Titanium 16,200 1.13 1.90 ND ND
*: In the table, Nn and Nw/Mn are number-average molecular weight and molecular weight distribution, respectively, determined by GPC as standard polystyrene-based values. Fn(v) represents the number of vinyl groups per molecule totally det~rm;nf~-l by from the results of GPC and NNR.
**: ND hereinafter indicates that the content of sodium and titanium falls below the minimum de~in~hle level , i . e ., 1 0 ppm .
Table 4 Solid base Nn Mw/Mn Fn (v) Sodium Titanium Ca(OH)2 16,900 1.16 1.80 ND ND
NaOCX3 16, 800 1.16 1. 83 ND ND
NaXCO3 16,300 1.17 1.44 ND ND
Table 5: Experiment on inactivation by water : ~
Nn Mw/Nn Fn (v) Sodium Titanium 16,500 1.15 1.82 ND ND
Table 6: F:~r~r;~ t on removal of halogenated hydrocarbon before inactivation of catalyst Mn Mw/Nn Fn (v) Sodium Titanium 9,500 3.49 0.92 ND ND
[ Preliminary examination 2 ] Experiment on selection of adsorbent ~ stirrer tip and a predetermined amount of an adsorbent were put into an Erlenmeyer f lask. The air in the f lask was then replaced by nitrogen . Methylene chloride (100 m~) was then charged into the flask so that the adsorbent was distilled therein. Titanium tetrachloride was then charged into the flask through a dried syringe, and the mixture was then stirred at room temperature for 1 hour. The solution (30 mQ ) was collected and then transferred to a separating f unnel . The solution was then washed with the same volume of ion-exchanged water three times. The three batches of wash water used were then put together. Ion-exchanged water was then added to the wash water to make 1,000 mQ. The wash water was then measured for pH by means of a pEI meter which had been previously corrected. The results are as shown in Table 7. It was found that activated carbon and aluminum silicate are highly capable of adsorbing an acid.
Table 7: ~rrnri ~ ~ t on selection of adsorbent Amount of Amount of titanium pH of wash Adsorbent adsorbent tetrachlorid water (g) (g) None 0 1.155 1. 97 Activated carbon 31. 2 0 . 980 4 . 60 Alumina oxide 36 . 0 1. 533 1. 88 Celite 17 . 9 1. 390 1. 81 Molecular sieves 3A 20 .1 0 . 803 1. 98 Aluminum silicate 7 . 0 0 . 921 3 . 8Z
[ Preparation example 2 ] Preparation of polymer solution ( 2 ) A 500 mQ-capacity pressure-resistant vessel equipped with a mechanical stirrer was thoroughly dried, and the air in the vessel was then thoroughly replaced by nitrogen. Into the vessel were then charged 187 mQ of methylene chloride which had been previously dehydrated with molecular sieves 3A, 125 mQ of n-hexane, 0.578 g of p-DCC and 0.047 g of a-picoline. The vessel was then cooled to a temperature of -50C. Isobutylene monomer (28 mQ) which had been measured out in a separate vessel was then transferred to the vessel.
Titanium tetrachloride ( 2 . 37 g) was charged into the vessel through a dried syringe while nitrogen gas was being introduced thereinto at a small rate through a three-way cock so as to initiate polymerization. Stirring was continued 21849~9 under the same conditions f or 2 hours to complete the reaction, and thus a polymer solution was obtained. The polymer solution obtained in th~ r~r~cnt preparation example will be hereinafter referred to as "polymer solution 2".
EXA~PI.E 7 Three dried f lasks equipped with a nitrogen line, a stirrer tip and a rectification column were prepared. The polymer solution 2 which had been kept at a temperature of -50C was then charged into these flasks in an amount of 40 g for each. Subsequently, activated carbon (available from Wako Pure Chemicals Co., Ltd.; finely divided powder) in an amount of 0.1 g, 0.5 g and 2.6 g, respectively, was then added into these f lasks . The mixture was then stirred under the same conditions f or 1 hour .
The flask was then dipped in a 45C oil bath so that methylene chloride was evaporated by rectif ication . The solid content was then removed by filtration with suction, and the content was then transferred to a separating funnel.
The resulting organic phase was then washed with 20 m~ of ion-exchanged water three times. The organic phase was then sub~ected to evaporation at a temperature o 120C under reduced pressure for 1 hour to obtain an isobutylene polymer.
The GPC and'NMR analysis data of the isobutylene polymer were as shown in Table 8 in which Fn indicates the number of functional groups per molecule. Table 8 also shows the results of analysis of the wash water.
Table 8: ~r~ri t with activated car~on as adsor~ent Amount of activated carbon Mn Mw/Mn Fn (iso) Fn (inn) DCM
(g) 2.6 8,100 1.24 0.11 0 ND
0.5 9,100 1.20 0.19 0.11 ND
0.1 7,700 1.43 ~ 0.15 0 ND
*: In the table, Mn and Mw/Mn indicate number-average molecular weight and molecular weight distribution, respectively, det-~rm;n~ by GPC. Fn (iso) and Fn (inn) indicate the number of isopropenyl groups and 2-methyl-1-propenyl groups per molecule, respectively. DCM indicates the content of methylene chloride in the wash water.
Experiments were conducted in the same manner as in Example 7 except that aluminum silicate was used in an amount of 0.1 g, 0.5 g and 2.6 g, respectively, instead of activated carbon to obtain isobutylene polymers. The results are shown in Table 9.
Table 9: Experiment with aluminum silicate as adsorbent Amount of aluminum silicate Mn Mw/Mn Fn ( iso ) Fn ( inn ) DCM
(g) 2.6 9,500 1.22 0 0 ND
0.5 9,400 1.20 0.09 0 ND
0.1 8,600 1.22 0.49 0.10 ND
In the same manner as in Example 7 except that no adsorbents were used, an isobutylene polymer was obtained.
The results are shown in Table 10.
Table 10: Comparative ~Yr~rir t free of adsorbent (1) Amount of adsorbent Mn Mw/Mn Fn (iso) Fn (inn) DCN
(g) 0 7,100 1.61 0.61 0.94 ND
COMPARATIVE EXAMPI,E 4 The polymer solution 2 (40 g) was poured into 100 g of methanol cooled with ice with vigorous stirring, and the solvent was removed by decantation. The resulting white precipitate was then re-dissolved in 30 m~ of n-hexane. The resulting organic phase was washed with ion-exchanged water three times. The material was then treated in the same manner as in Example 7 to obtain an isobutylene polymer. The results are shown in Table 11.
Table 11: Comparative ~YrPri - t free of adsorbent (2) Mn ~w/Mn Fn (iso) Fn (inn) 8,700 1.29 0 0 The cold methanol reprecipLtation method shown in Table 11 can produce a sample with least side reactions in laboratory isolation methods, but produces a mixed solvent which is difficult to purify. It has been found that such a polymer has a tertiary carbon-chlorine bond at the ends thereof. Therefore, the fact that Fn (iso) and Fn (inn) in Table 11 are each O indicates that no isomerization occurs at the ends of the polymer. In the method free of adsorbent shown in Table 10, the molecular weight distribution is increased with the progress of isomerization at the ends of the polymer, demonstrating that undesirable side reactions occur. The ~ r; ~on between Tables 8 and 9 shows that as the content of the adsorbent decreases, the results is close to that of the case using no adsorbent. Since methylene chloride had been removed bef ore washing with water in Tables 8 and 9, methylene chloride could not be detected in the wash water .
[ Industrial applicability]
As compared with the prior art, the process of the present invention has the following advantages:
1. Even if a halide such as methylene chloride is used as a solvent for the polymerization of isobutylene monomer, no waste water having such a halide dissolved therein is generated.
2. The washing step can be omitted from the standpoint of process mechanism.
3. The dehydrochlorination reaction at the ends of the polymer at the same time with the ligand exchange reaction makes it possible to easily obtain a telechelic isobutylene polymer having unsaturated groups without isolating a telechelic polymer terminated by chlorine group as an int~ te.
4. The dehydrochlorination reaction at the ends of the polymer under reduced pressure makes it possible to accelerate the polymerization reaction.
( 1 ) a cationically poly - 7~hle monomer having isobutylene;
( 2 ) a compound represented by the f ollowing general formula (III):
~3 ( I I I ) wherein Rl represents an aromatic ring group or substituted or unxubstituted aliphatic hydrocarbon group; R2 and R3 may be the same or different and each represent a hydrogen atom or substituted or unsubstituted monovalent hydrocarbon group, with the prQViso that when Rl is an aliphatic hydrocarbon group, at least one of R2 and R3 is not a hydrogen atom; X
reprexents a halogen atom, R4Coo- group (in which R4 reprexents a hydrogen atom or a Cl 5 alkyl group) or R50-group (in which R5 l~:ul~su-lLs a llyd- U~l atom or a Cl 5 alkyl group ); and w represents an integer of f rom 1 to 8;
(3) a catalyst represented by the foregoing general formula (I);
( 4 ) an electron donor component having a donor number of from 15 to 50; and ( 5 ) a reaction solvent .
In general, when the ligand exchange reaction is effected in the presence of a compound represented by the foregoing general formula ( II ), a small amount of a compound represented by the general formula GOH [in which G represents a llydlvy~ll atom or a monovalent hydrocarbon group ] can be used as a catalyst. For example, CH30H, CH3CH20H, (CH3)2CHOH, a slight amount of water, etc. may be used.
The term "non-aqueous system" as used herein does not necessarily mean a system which employs no water but means a system which generates no waste water. If necessary, an extremely small amount of water may be added to cause the ligand exchange reaction of the catalyst to proceed smoothly.
In such a case, the water thus added is adsorbed by the adsorbing material capable of adsorbing an acid in the reaction solution, thus generating no waste water.
In the present invention, the isobutylene polymer normally has a number-average molecular weight (Mn) of from 500 to 300,000, preferably from 1,000 to 50,000. If ~n is less than 500, the excellent characteristics inherent to isobutylene polymer are lost. On the contrary, if Mn exceeds 300,000, the resulting polymer is solid, extremely 2i84999 deteriorating the workability thereof. The number-average molecular weight (Mn) and Mw/Mn value of the isobutylene polymer were determined by GPC using a polystyrene gel column [Shodex K-804, available from Showa Denko R.E~.; mobile phase:
chloroform] as a polystyrene-based value.
As the catalyst component represented by the foregoing general formula (I) for the present invention, any metallic complex known as Lewis acid may be used without any restriction. In general, TiC14, SnCl4, AlC13, CH3CX2AlC12, (CH3CH2)2AlCl, VCl5, FeCl3, BF3, etc. may be used. However, the catalyst ~ t is not limited to these compounds.
Among these Lewis acids, TiCl4, SnCl4, and AlCl3 are pref erable .
In the present invention, the Lewis acid is normally used in an amount of from 0.1 to 10096 by weight, preferably from 1 to 309~ by weight based on the weight of the cationically poly 7~hle monomer having isobutylene. If the amount of the Lewis acld to be used as a catalyst component is less than 0.196 by weight, the yield of the cationic polymerization reaction decreases. On the contrary, if the amount of the Lewis acid to be used exceeds 10096 by weight, no f urther merits can be obtained .
As the compound represented by the f oregoing general formula (II) for the present invention, any ~ d containing a metallic atom belonging to the group I., II~, IIIb or IV" of the periodic table may be used without any restriction. In general, NaOH, ROH, LiOH, Ca(OH)2, NaHCO3, NaOCH3, KOCH3, LiOCH3, Ca ( OCH3 ) 2, Mg ( OCH3 ) z, Al ( OCH3 ) 3, Ti ( OCH3 ) 4, NaOCH2CH3, KOCH2CH3, LiOCH2CH3, Ca ( OCH2CH3 ) 2 r Mg ( OCH2CH3 ) 2, Al ( OCH2CH3 ) 3, Ti ( OCH2CH3 ) 4, NaOC ( CH3 ) 3, ROC ( CH3 ) 3, LiOC(CH3)3, NaOC(CH3)2CH2CH3, Al[OCH(CH3)2]3, etc. may be used.
Among these compounds, NaOC~3, KOCH3, NaOH, KOH, and NaOCHzCH3 are pref erable .
In the present invention, the compound represented by the general formula ( II ) is normally used in an amount of from 0.1 to 100 mol, preferably from 2 to 20 mol per 1 mol of the catalyst component represented by the foregoing general formula (I). If the amount of the compound represented by the general formula (II) to be used is less than 0.1 mol per mol of the catalyst component, the separation of the polymer from the catalyst is difficult. On the contrary, if the amount of the compound represented by the general f ormula ( II ) to be used exceeds 100 equivalents, no further merits can be obtained.
In the present invention, the ligand exchange reaction is normally effected under normal pressure or reduced pressure at a temperature of from -100C to 150C for 1 to 600 minutes. In the present invention, the removal of the Lewis acid catalyst after the ligand exchange can be a- ~ li fih~d by filtration, if the metallic complex derived from the catalyst is solid, or by distillation under reduced pressure, if the metallic complex derived from the catalyst _ 9 _ is liquid. However, the present invention is not limited to these methods, and any methods are practicable.
In the present invention, as the adsorbing material capable of adsorbing an acid for use in the removal of the catalyst, compounds mainly composed of at least one of ~-activated carbon, titanium oxidej Mg, Al and/or Si may be used. E:xamples of such a compound containing Si include aluminum silicate ( silica alumina ), molecular sieves (zeolite), silica gel, alumina gel, and activated clay.
Among these adsorbing materials, activated carbon and aluminum silicate are preferable.
In the present invention, the adsorbing material capable of adsorbing an acid is normally used in an amount of from 0.2 to 300 times, preferably from 3 to lO0 times the weight of the compound represented by the f oregoing general f ormula ( I ) . The temperature at which adsorption is ef f ected is normally from -100C to 40C, preferably from -70C to 25C. The reaction time is normally from I second to 10 hours .
In the present invention, the cationically polymerizable monomer containing isobutylene is not limited to a monomer made of isobutylene alone. The cationically poly 7~hle monomer containing isobutylene of the present invention contains a monomer copoly 7Ahle with isobutylene, preferably in an amount of not more than 5096 by weight (hereinafter simply referred to as "96 ' ) .
_ 10 --, .
Examples of the cationically polymerizable monomer copolymerizable with isobutylene include C3 l2 olefins, con~ugated dienes, vinyl ethers, aromatic vinyl compounds, norbornenes, and vinyl silanes. Amony these cationically poly 7;lhle r~n~ ~ C3 lz olefins and aromatic vinyl compounds are pref erable .
Specific examples of the cationically polymerizable monomer copolymerizable with isobutylene usually include propene, 1-butene, 2-butene, 2-methyl-1-butene, 3-methyl-1-butene, pentene, hexene, cyclohexene, vinylcyclohexane, 5-ethylidenenorbornene, 5-propylidenenorbornene, butadiene, isoprene, cyclopentadiene, methyl vinyl ether, ethyl vinyl ether, isobutyl vinyl ether, vinyl carbazole, methu.~y~LyLe-~e, ethu~y~l~y~ e~ t-butu~y~l yL~IIe~ hexenyloxy styrene, styrene, a-methylstyrene, methylstyrene, dimethylstyrene, chloromethylstyrene, chlorostyrene, indene, ,~-pinene, vinyltrichlorosilane, vinylmethyldichlorosilane, vinyldimethylchlorosilane, vinyldimethylmethoxysi1ane, vinyltrimethylsilane, divinyldichlorosilane, divinyldimethoxysilane, divinyldimethylsilane, 1,3-divinyl-1,1, 3, 3-tetramethyldisiloxane, trivinylmethylsilane, y-methacryloylu~y~Lu~yltrimethoxysilane~ and y-methacryloylu~y~Lu~ylmethyldimethoxysilane .
Among these cationically poly z~hle - I s, propene, l-butene, 2-butene, cyclopentadiene, 5-ethylidene norbornene, isobutyl vinyl ether, methoxystyrene, and styrene and the like are preferable. One of these cationically poly -~ 7Ahle monomers copolymerizable with isobutylene may be used in combination with isobutylene, and two or more of these cationically poly 7Ahle monomers may be used in combination .
In the present invention, the concentration of the cationically poly - - 7Ahle monomer containing isobutylene in the batch process is normally from 0.1 to 10 mol/Q, preferably from 0.5 to 6 mol/Q.
Examples of the compound represented by the f oregoing general formula (III) of the present invention include a compound represented by the following general formula (IV):
AY, ( IV ) wherein A represents a group having l to 4 aromatic rings, n represents an integer of from l to 8, and Y represents a group represented by the following general formula (V):
lR6 wherein R6 and R7 may be the same or dif f erent and each represent a hydrogen atom or a Cl 20 monovalent hydrocarbon group, and X represents a halogen atom, a R4Coo- group (in which R4 represents a hydrogen atom or Cl 5 alkyl group) or a R50- group (in which R5 represents a hydrogen atom or a Cl 5 alkyl group); a compound represented by the following general formula (VI ):
BZD, (VI ) wherein B represents a C4 40 substituted or unsubstltuted hydrocarbon group, Z represents a halogen atom connected to the tertiary carbon atom, a R8C00- group (in which R8 represents a hydrogen atom or a Cl 5 alkyl group) or a R90-group (in which R9 represents a' hydrogen atom or a Cl 5 alkyl group ), and m represents an integer of f rom 1 to 4 ; and an oligomer having cL-halostyrene units, but are not limited to these compounds. These compounds may be used alone or in combination of two or more.
In the compound represented by the general formula ( IV), the group having 1 to 4 aromatic rings represented by A
may be produced by conllPn~tion reaction or may not be a condensation product. Examples of the group containing aromatic rings include groups having a valence of ~rom 1 to 6 which is derived from benzene, biphenyl, naphthalene, anthracene, phenanthrene, pyrene, Ph- ( CEI2 ) l-Ph ( in which Ph represents a phenyl group, and 1 represents an integer of from 1 to 10 ) . These groups having aromatic rings may be substituted by Cl 20 straight and/or branched aliphatic hydrocarbon groups or groups containing a functional group such as a hydroxyl group, an ether group and a vinyl group.
As the compound represented by the general formula (VI ), compounds having a functional group other than z, such as vinyl group and silyl group, may be used.
218~999 Examples of the oligomer having c~-halostyrene units which can be used as the initiator/chain transfer agent include oligomer of ~-chlorostyrene, and oligomer obtained by the copolymerization of ~-chlorostyrene with a monomer copolymerizable with styrene.
In the present invention, it is advantageous to use, among the compounds represented by the general formula (III), a compound having two or more of halogen atoms, R4Coo- groups (in which R4 represents a hydrogen atom or a Cl 5 alkyl group) or R50- groups ( in which R5 represents a hydrogen atom or a Cl 5 alkyl group) or a compound having a halogen atom, a R4Coo- group or a R50- group together with reactive functional groups as an initiator/chain transfer agent since the resulting polymer has a higher functionality.
Specif ic examples of the compound represented by the foregoing general formula (III) which can be normally employed include the following compounds:
X--C~ ICH - 3X X--C~ C(CH333 CX(CH3)2 Cx(cH3)2 X--C ~ CH~ Cl H - X
CH3 CX(CH3)2 CH3 CH3 218~999 CH3~C--X X--C~CH2CH2~ IH - 3X
CH3 CHl CH3 CHJ
X--C~CH2CH2CH2 ~ ICH - X
CH3 CH3 Cl H3 (n-c8H17) (n-c8H17) CH3 CH3 ICH3 X--c--CH2CH2CH2CH2--C--X X--C--CH2CH2--C--CH2CH2--C--X
(n-CsH17) (n-CsH17) CH
H2C=CH-CH2CH2CH2CH2-- ~ CH2--X H2C=CH-CH2CH2CH2CH2--C--X
H
H2C=CH-CH2CH2CH2CH2-- ~ C--X
wherein X represents a halogen atom, a R4Coo- group ( in which R4 represents a hydrogen atom or a C1 5 alkyl group) or a R50-group (in which R5 represents a hydrogen atom or Cl 5 alkyl group), and oligomer of ~-chlorostyrene, but are not limited to these compounds . Among these compounds, pref erable ones are:
218~999 .
Cl--C~ C--Cl Br--C ~ C--~r CH3 Ccl(cH3)2 CH3 C(CH3)3 Cl-C~ Cl-C~
CH3 Ccl(cH3)2 CCI(CH3)2 Cl C ~ CH2CH2 ~ C--Cl Cl--C ~ CH2cH2cH2 ~g~ l H - Cl Cl--C--C--Cl CH3 CH3 . CH3 CH3 Cl--C--CH2CH2--C--CH2CH2--C--Cl Hzc=cH-cH2cH2cH2cH2--O~CH2--Cl H2c=cH-cH2cH2cH2cH2--C--Cl H
H2c=cH-cH2cH2cH2cH2-- ~ C--Cl -- 218~999 C~3COO- group-containing compounds such as O
o CH3 CH3 I CH3 0 CH3 C=O CH3 CH3~0 --C~C--OCCH3 CH3l~0--C~C(CHI)2 O~CH
C(CH3)2 o CCH
and C~I30- group-containing compounds such as CHl CH3 CH3 CH3 rCH3 CH30--C--CH2--O--CH2--C--OCH3 CH30--C ~ C--OCH3 CH~ ( 2 3 CH3 C(CHI320CH3 These compounds are components which are used as initiators/chain transfer agents. These cl ~ u-Lds may be ~ 2184999 used alone or as a mixture of two or more in the present invention. By controlling the amount of these compounds to be used, the number-average molecular weight of the resulting isobutylene polymer can be arbitrarily predetF~nni n~d.
In the present invention, the amount of the compound represented by the foregoing general formula (III) to be used is normally from 0.01 to 20~ by weight, preferably from 0.1 to 10% by weight based on the weight of the cationically polymerizable monomer containing isobutylene.
As the electron donor component f or the present invention, any known electron donor components having a donor number of from 15 to 50 may be used. Preferred examples of such electron donor components include pyridines, amines, amides, and sulfoxides, but are not limited to these compounds .
Specific examples of the electron donor component for the present invention include 2,6-di-t-butylpyridine, 2-t-butylpyridine, 2, 4, 6-trimethylpyridine, 2, 6-dimethylpyridine, 2-methylpyridine, pyridine, diethy1amine, trimethylamine, triethylamine, tributylamine, diethylamine, N,N-dimethylaniline, N,N-dimethylformamide, N, N-dimethylacetamide, N, N-diethylacetamide, dimethylsulfoxide, diethyl ether, methyl acetate, ethyl acetate, trimethyl phosphate, and hexamethylphosphoric triamide. Among these electron donor ~ n~ntS, 2,6-di-t-butylpyridine, 2, 6-dimethylpyridine, 2-methylpyridine, 218~999 pyridine, diethylamine, trimethylamine, triethylamine, N,N-dimethylformamide, N,N-dimethylacetamide, and dimethylsulfoxide are preferable. Picolines are further pref erred . Among these electron donors, 2-methylpyridine is particularly preferred since a L` rk~hle effect can be obtained even with its small donor number.
In the present invention, the electron donor component is normally used in an amount of from O . 01 to 10 mol, preferably from 0.1 to 2 mol per mol of the compound represented by the general formula (III).
As the reaction solvent for the present invention, halogenated hydrocarbons, aliphatic hydrocarbons, aromatic hydrocarbons or the like may be used. Examples of the halogenated hydrocarbon include methyl chloride, methylene chloride, 1, l-dichloroethane, 1, 2-dichloroethane, 1-chloropropane, 1-chloro-2-methylpropane, 1-chlorobutane, l-chloro-2-methylbutane, l-chloropentane, l-chlorohexane, and l-chloro-2-methylhexane. Examples of the aliphatic or aromatic hydrocarbon include butane, pentane, neopentane, hexane, cyclohexane, methylcyclohexane, heptane, octane, benzene, toluene, and xylene.
Examples of the mixed solvent which can be used in the pre6ent invention include various combinations such as methylene chloride/hexane, 1, 2-dichloroethane/hexane, l-chlo~opLu~d~le/hexane, l-chlorobutane/hexane and 1 -chloropentane/hexane .
~ 218~999 In the present invention, the polymerization reaction is not specif ically limited and can be carried out by any conventional polymerization method. Among the foregoing components, i . e ., ( 1 ) a cationically polymerizable monomer having isobutylene, (2) a compound represented by the general formula (III), (4) a Lewis acid, and (5) an electron donor component, a solution containing (4) a Lewis acid may be added to a solution containing a cationically poly - 7~hle monomer containing lsobutylene in a batch process.
Alternatively, a solution containing ( 1 ) a cationically poly ri 7~hle monomer containing isobutylene may be continuously added to a solution containing ( 4 ) a Lewis acid in a semi-batch process. Further, a continuous process may be employed in which all the foregoing components are continuously charged into the reaction system while removing the reaction product.
In the present invention, if the ligand exchange reaction of the catalyst represen~ed by the foregoing general formula ( I ) is accompanied by the dehydrochlorination reaction at the ends of the polymer, any compounds represented by the foregoing general fo~mula ( II ) may be used without any restriction. Preferred examples of such a ~ u~ld include NaOH, ROH, LiOH, Ca(OH)2, NaHCO3, NaOCH3, ~OCH3, LiOCH3, Ca ( OCH3 ) z, NaOCH2CH3, ROCH2CH3, LiOCH2CH3, NaOC ( CH3 ) 3, ROC ( CH3 ) 3, 1: iOC ( CH3 ) 3, NaOC ( CH3 ) zCHzCH3, and Al[OCH(CH3)2]3 -218~999 In the present invention, if the ligand exchange reaction of the catalyst represented by the foregolng general formula (I) is accompanied by the dehydrochlorination reaction at ~he ends of the polymer, the dehydrochlorination reaction is preferably effected under reduced pressure. The dehydrochlorination reaction is normally ef f ected under a pressure of not higher than 700 mmHg, preferably not higher than 20 ml~3Hg, and more preferably not higher than 1 mmHg. A
process for the preparation of an isobutylene polymer having telechelic unsaturated groups in the presence of NaOC~3, ~OC(CH3)3 or the like under normal pressure has already been known. However, the reaction under normal pressure is disadvantageous in that the reaction rate is actually low.
In particular, it takes from 20 to 30 hours to complete the reaction at temperatures of not higher than 100C [see examples described in U.S. Patent No. 4,316,973 and JP-A-1-261405]. Then, the inventors made extensive studies and, as a result, it was f ound that the dehydrochlorination reaction can be accelerated by reducing the pressure of the reaction system. The dehydrochlorination reaction at the ends of the polymer is considered to be an E2 reaction from the st~n~lr~int of reaction mechanism. Further, this elimination reaction is considered to be an irreversible reaction. Thus, it hardly can be considered in common sense that this reaction can be accelerated under reduced pressure.
Accordingly, it can be said that an unexpected effect appeared. The reaction temperature at which the dehydrochlorination reaction occurs is normally from 30C to 300C, preferably from 60C to 200C. If possible, the reaction is preferably effected~ with stirring without solvent .
[Best Mode for Carrying out the Invention]
The present invention will be further described in the following examples, but the present invention should not be construed as being limited thereto.
Structural analysis of isobutylene polymer The structure of the isobutylene polymer obtained in the examples was determined by IH-NMR spectrometry and GPC
analysis. The measuring instruments used and the conditions for mea~ul~ ts will be given below.
H-NMR spec~rometry (300 MHz): Gemini-300, available from Varian Corp. (measured in a mixture of heavy acetone and carbon tetrachloride ) GPC analysis: System: System available from Waters Corp. (Pump 600E, Differential Refractometer 401, etc. ) Column: Shodex-804 (polystyrene gel), available from Showa Denko K.~t.
~ 2184999 Mobile phase: chloroform (number-average molecular weight, etc. are de~rmi n~d as a polystyrene-based value ) The air in a 200 mQ-capacity pressure-resistant glass vessel equipped with a magnetic stirrer and a three-way cock was replaced by nitrogen. Into the vessel were charged 5g mQ
of methylene chloride (which had been allowed to stand overnight or longer with molecular sieves 3A for drying), 37 mQ of hexane (which had been allowed to stand overnight or longer with molecular sieves 3A for drying), and 0.139 g (0.6 mmol) of 1,4-bis(c~-chloroisopropyl)benzene [p-DCC]
through a syringe. Then, a pressure-resistant liquefied gas-collecting glass tube equipped with a needle valve in which 8 mQ (96 mmol) of iso~utylene monomer had been charged was connected to the three-way cock. The polymeri2ation vessel was then dipped in a -70C dry ice/ethanol bath for cooling.
The air was then evacuated from the vessel by a vacuum pump.
The needle valve was then opened so that the isobutylene monomer was introduced from the liquefied gas-collecting tube into the polymerization vessel. Nitrogen gas was then introduced into the polymerization vessel from one of the three ways of the cock so that the pressure of the vessel was returned to normal value. A methylene chloride solution (1 ml containing 11.2 uQ (0.12 mmol) of 2-methylpyridine was ~ 218~999 added into the polymerization vessel, and stirring of the monomer solution was then started at a temperature of -70C.
A methylene chloride 801utLon ( 3 me ) containing 0.33 me (3 mmol) of titanium tetrachloride was then added to the polymerization solution through a syringe to initiate cationic polymerization reaction. The polymerization solution was allowed to undergo cationic polymerization reaction at a temperature of -70C for 60 minutes.
Thereafter, 5.8 g of a methanol solution of 1.62 g (30 mmol) of sodium methoxide (sodium methoxide content: 28%) was added to the polymerization solution at -70C. The polymerization vessel was withdrawn from the dry ice/ethanol bath, and then dipped in a hot water bath so that the temperature of the polymer solution was raised to 40C. The polymer solution was then moved into a 300 me-capacity eggplant-type f lask . The volatile content was then removed at a temperature of 100C under reduced pressure (not higher than 1 mm~Ig ) by means of an evaporator in 2 hours . EIexane (200 me) was then charged into the eggplant-type flask to dissolve the isobutylene polymer. The solution was then filtered through a Kiriyama funnel filter paper (No. 4;
retained particle: 1 llm) with suction. The volatile content was then evaporated to obtain 6.1 g of a colorless transparent isobutylene polymer. The properties of the polymer thus ob~ained are shown in Table 1.
Ti and Na, which are considered to be contaminating the polymer, were then determined. The results of the analysis are also shown in Table 1.
Into a le-capacity separable flask equipped with a mechanical stirrer and a three-way cock was charged 1. 65 g ( 7 .14 mmol ) of p-DCC. The air in the vessel was then replaced by nitrogen, and 83 mQ of methylene chloride (which had been allowed to stand overnight or longer with molecular sieves 3A for drying) and 174 mQ of hexane (which had been allowed to stand with molecular sieves 3A overnight or longer for drying) were then added to the polymerization system through a syringe.
To the three-way cock was then connected a liquefied gas-collecting pressure-resistant glass tube equipped with a needle valve in which 85.5 mQ of isobutylene monomer had been charged. The polymerization vessel was then dipped in a -75 C dry ice/ethanol bath f or cooling . The air was then evacuated from the vessel by a vacuum pump. The needle valve was then opened so that the isobutylene monomer was introduced from the liquefied gas-collecting tube into the polymerization vessel. Nitrogen gas was then introduced into the polymerization vessel from one of the three ways of the cock so that the pressure of the vessel was returned to normal value. A solution obtained by diluting O.133 g (1.43 mmol) of rY-picoline [2-methypyridine] with 1 mQ of methylene chloride was then added into the polymerization vessel. The monomer solution was then stirred at a temperature of -75CC by means of a mechanical stirrer. ~ --~
A solution obtained by diluting 1.04 m~ (9.52 mmol) of titanium tetrachloride with 12 mQ of methylene chloride was then added into the polymerization vessel. The polymerization system was then allowed to undergo polymerization reaction at a temperature of -75C for 60 minutes. Thereafter, 8.5 mQ (114 mmol) of methanol and 5.39 g (100.0 mmol) of sodium methoxide were added to the polyisobutylene (PIB) solution at -75C, followed by stirring. The polymerization vessel was withdrawn from the dry ice/ethanol bath, and then dipped in a hot water bath so that the temperature of PIB solution was raised to about 4o C .
The vessel was then dipped in a 50C oil bath. The volatile content was evaporated under normal pressure and under reduced pressure while the temperature of the system was being gradually raised to 100C. The mixture of PIB and a white powder which had Ll ;notl in the vessel was then stirred for 60 minutes by means of the mechanical stLrrer under reduced pressure ~not higher than 1 mmHg, evacuated by a vacuum pump) while the system was being heated to a temperature of 100C. IIexane (500 mQ) was then added into the vessel to dissolve PIB. The solution was filtered through a Kiriyama f ilter paper to recover a solid content .
218~999 Hexane was then evaporated to obtain 57 . 4 g of an isu~Lu~ yl-terminated PIB. The properties of the polymer thus obtained are shown in Table 1.
Table l GPC 96, Proportion ElementarY analYsis r96) of isu~luy~
Mn Mw/Mn groupl) at end Ti2) Na3) Example l 11300 1.22 gl c 0.001 c 0.001 Example 2 8800 1. 37 94 -- -- =
1 ) Isopropenyl group: -CX2C ( CH3 ) =CH2 2) The sample was wet-decomposed, and then detprminl~d by ICP
emission spectroscopic analysis.
3) The sample was dry-decomposed, and then det~rmin--fl by atomic absorption spectroscopy.
The resuLts set forth in Table 1 show that the isobutylene polymers obtained in Examples 1 and ~ contain little or no Ti or ~a. Thus, it is clear that high purity polymers containing little or no impurities were obtained.
Table 1 also shows that the processes of Examples 1 and 2 are processes for the effective preparation of an isopropenyl-terminated isobutylene polymer.
[PrF~l iminAry Examination 1] Measurement of water absorption of metal oxide Titanium oxide ( 1. 00 g) (available from Wako Pure Chemicals Co., Ltd. ) was weighed in a ground glass Erlenmeyer flask which had been thoroughly dried. Then, 91.6 g (100 mQ) of a 4/6 (by volume) mixture of methylene chloride and n-hexane and a predetermined amount of water were added, and the reaction mixture was then stirred at room temperature for I hour. The resulting slurry was then filtered through a No.
4 Kiriyama filter paper with suction. Free water in the f iltrate was then measured by the Karl Fischer moisture meter .
The water content in the air, the water content which had previously been adsorbed by titanium oxide and the water content in the mixed solvent were determined by blank test.
The water content in the filtrate was then de~ nl~d by subtracting these water contents f rom measured value . The results are shown in Takle 2. It was found that when the weight of the water content adsorbed by titanium oxide is up to 1. 5 times greater than that of titanium oxide, the filtrate is not separated into two phases.
[ Preparation Example 1 ] Preparation of polymer solution ( l ) A pressure-resistant vessel equipped with a mechanical stirrer was thoroughly dried, and the air in the vessel was thoroughly replaced by nitrogen. Into the vessel were then charged 112 mQ of methylene chloride which had been previously dehydrated through molecular sieves 3A, 173 mQ of n-hexane, 0 . 289 g of p-DCC and 0 . 047 g of ~-picoline . The vessel was then cooled to a temperature of -70C, 28 mQ of an isobutylene monomer was then transferred to the vessel.
'~ 21'84~g9 Then, 6.83 g (36 mmol) of titanium tetrachloride was added through a dried syringe while nitrogen was being introduced at a small rate through a three-way cock so as to initiate polymerization. The polymerization system was stirred at the same temperature for 1 hour. To the polymerization system was then added 9.96 g of 1,9-decadiene. The polymerization system was further stirred for 4 hours to introduce a carbon-carbon double bond into the ends of the polyisobutylene. The polymer solution obtained in the present Preparation Example will be hereinafter referred to as "polymer solution l".
EXA~PLE 3 Into an eggplant-type flask was charged 32.4 mQ
(159 mmol) of a 4.90 N methanol solution of sodium methoxide.
The polymer solution 1 at a temperature of -70C was then slowly poured into the polymerization sy~tem. The polymerization system was then stirred until the temperature of the content was returned to room temperature, i.e., for 30 minutes. The flask was then dipped in a 100C oil bath, the solvent was then evaporated under reduced pressure. After 15 minutes, the f lask was removed the evaporator . The content of the flask was then washed with 50 mQ of n-hexane twice to dissolve the polymer therein. The slurry containing a polymer solution was then filtered through a No. 4 ~iriyama filter paper with suction. The resulting transparent filtrate was heated over a 130C oil bath under reduced pressure for 1 hour to isolate 18 . 8 g of a polymer.
The GPC and NMR analysis of the polyisobutylene obtained are shown in Table 3. The results of atomic absorption spectroscopy o~ sodium and ICP analysis of titanium in the polymer are also shown in Table 3.
EXA~P1E 4 Into a flask were charged 11.78 g (159 mmol) of calcium hydroxide and 3 . 0 g of water. The polymer solution 1 at a temperature of -70C was then poured into the polymerization system. The polymerization system was then stirred at room temperature f or 3 hours . The resulting slurry content was then filtered through a No. 4 filter paper with suction. To the resulting filtrate was then added 1 g of aluminum silicate. The mixture was then stirred at room temperature f or 3 hours, and then f iltered through a No . 4 ~iriyama filter paper with suction. The filtrate was then sub~ected to evaporation under reduced pressure in the same manner as in Example 3 to isolate a polymer. The polymer thus obtained will be hereinafter referred to as ~polymer 2".
The results of GPC and Nr~R analysis of the polymer 2 are shown in Table 4 with the results of determination of sodium and titanium in the polymer 2.
EXA~PI.E 5 In the same manner as in Example 4 except that 8.59 g of a sodium methoxide powder was used instead of calcium hydroxide, a polymer was lsolated. The results are shown in Table 4.
2184~
In the same manner as in Example 4 except that 13 . 36 g of a sodium hydrogencarbonate powder was used instead of calcium hydroxide, a polymer was isolated. The results are shown in Table 4.
COMPAR~TIVE E~AMPLE 1 The polymer solution 1 at a temperature of -70C was poured into 300 m~ of water to inactivate a catalyst. The aqueous phase was then removed by decantation, and the inin~ organic phase was then repeatedly washed with 300 me of ion-exchanged water until the electrical conductance of the waste water reached constant. For this purpose, washing was needed three times. As a result, 1, 200 m~ of waste water containing methylene chloride and n-hexane in a saturated concentration was generated.
The waste water was then subjected to evaporated under reduced pressure in the same manner as in Example 3 to isolate a polymer. The results of analysis of the polymer are shown in Table 5.
The polymer solution 1 was heated in a 45C bath to evaporate methylene chloride. The generation of hydrogen chloride was recognized during heating. Thus, a serious corrosion occurred in the gas phase area of a metallic vessel (material: SUS316L). When the distillation was stopped, the .
21849~9 content of the vessel was poured into 300 m~ of water, and washing with water was repeated three times.
The material was then subjected to evaporation under reduced pressure in the same manner as in Example 3 to isolate a polymer. The results of analysis are shown in Table 6.
Table 2: Water absorption of metal oxide Titanium Amount of Water/titanium Water content Filtrate oxide water added oxide ratio in f iltrate Condition (mg) (mg) (mol/mol) (ppm) 984.1 505.9 2.28 225 994 . 0 756 . 0 3 . 38 226 994.0 1006.0 4.4g 244 994.0 1506.0 6.72 214 991.5 2008.5 8.99 355 +
991.5 2508.5 11.23 435 +
1051 . 0 3009 . 0 12. 71 441 +
1011.3 4008.7 17.59 448 +
994 . 0 5006 . 0 22 . 35 415 +
1001.4 7008.6 31.07 451 +
Note) --: The filtrate was uniform.
+: The f iltrate was separated into two phases: aqueous phase and organic phase.
218~999 Table 3 Mn Mw/Nn Fn(v) Sodium i Titanium 16,200 1.13 1.90 ND ND
*: In the table, Nn and Nw/Mn are number-average molecular weight and molecular weight distribution, respectively, determined by GPC as standard polystyrene-based values. Fn(v) represents the number of vinyl groups per molecule totally det~rm;nf~-l by from the results of GPC and NNR.
**: ND hereinafter indicates that the content of sodium and titanium falls below the minimum de~in~hle level , i . e ., 1 0 ppm .
Table 4 Solid base Nn Mw/Mn Fn (v) Sodium Titanium Ca(OH)2 16,900 1.16 1.80 ND ND
NaOCX3 16, 800 1.16 1. 83 ND ND
NaXCO3 16,300 1.17 1.44 ND ND
Table 5: Experiment on inactivation by water : ~
Nn Mw/Nn Fn (v) Sodium Titanium 16,500 1.15 1.82 ND ND
Table 6: F:~r~r;~ t on removal of halogenated hydrocarbon before inactivation of catalyst Mn Mw/Nn Fn (v) Sodium Titanium 9,500 3.49 0.92 ND ND
[ Preliminary examination 2 ] Experiment on selection of adsorbent ~ stirrer tip and a predetermined amount of an adsorbent were put into an Erlenmeyer f lask. The air in the f lask was then replaced by nitrogen . Methylene chloride (100 m~) was then charged into the flask so that the adsorbent was distilled therein. Titanium tetrachloride was then charged into the flask through a dried syringe, and the mixture was then stirred at room temperature for 1 hour. The solution (30 mQ ) was collected and then transferred to a separating f unnel . The solution was then washed with the same volume of ion-exchanged water three times. The three batches of wash water used were then put together. Ion-exchanged water was then added to the wash water to make 1,000 mQ. The wash water was then measured for pH by means of a pEI meter which had been previously corrected. The results are as shown in Table 7. It was found that activated carbon and aluminum silicate are highly capable of adsorbing an acid.
Table 7: ~rrnri ~ ~ t on selection of adsorbent Amount of Amount of titanium pH of wash Adsorbent adsorbent tetrachlorid water (g) (g) None 0 1.155 1. 97 Activated carbon 31. 2 0 . 980 4 . 60 Alumina oxide 36 . 0 1. 533 1. 88 Celite 17 . 9 1. 390 1. 81 Molecular sieves 3A 20 .1 0 . 803 1. 98 Aluminum silicate 7 . 0 0 . 921 3 . 8Z
[ Preparation example 2 ] Preparation of polymer solution ( 2 ) A 500 mQ-capacity pressure-resistant vessel equipped with a mechanical stirrer was thoroughly dried, and the air in the vessel was then thoroughly replaced by nitrogen. Into the vessel were then charged 187 mQ of methylene chloride which had been previously dehydrated with molecular sieves 3A, 125 mQ of n-hexane, 0.578 g of p-DCC and 0.047 g of a-picoline. The vessel was then cooled to a temperature of -50C. Isobutylene monomer (28 mQ) which had been measured out in a separate vessel was then transferred to the vessel.
Titanium tetrachloride ( 2 . 37 g) was charged into the vessel through a dried syringe while nitrogen gas was being introduced thereinto at a small rate through a three-way cock so as to initiate polymerization. Stirring was continued 21849~9 under the same conditions f or 2 hours to complete the reaction, and thus a polymer solution was obtained. The polymer solution obtained in th~ r~r~cnt preparation example will be hereinafter referred to as "polymer solution 2".
EXA~PI.E 7 Three dried f lasks equipped with a nitrogen line, a stirrer tip and a rectification column were prepared. The polymer solution 2 which had been kept at a temperature of -50C was then charged into these flasks in an amount of 40 g for each. Subsequently, activated carbon (available from Wako Pure Chemicals Co., Ltd.; finely divided powder) in an amount of 0.1 g, 0.5 g and 2.6 g, respectively, was then added into these f lasks . The mixture was then stirred under the same conditions f or 1 hour .
The flask was then dipped in a 45C oil bath so that methylene chloride was evaporated by rectif ication . The solid content was then removed by filtration with suction, and the content was then transferred to a separating funnel.
The resulting organic phase was then washed with 20 m~ of ion-exchanged water three times. The organic phase was then sub~ected to evaporation at a temperature o 120C under reduced pressure for 1 hour to obtain an isobutylene polymer.
The GPC and'NMR analysis data of the isobutylene polymer were as shown in Table 8 in which Fn indicates the number of functional groups per molecule. Table 8 also shows the results of analysis of the wash water.
Table 8: ~r~ri t with activated car~on as adsor~ent Amount of activated carbon Mn Mw/Mn Fn (iso) Fn (inn) DCM
(g) 2.6 8,100 1.24 0.11 0 ND
0.5 9,100 1.20 0.19 0.11 ND
0.1 7,700 1.43 ~ 0.15 0 ND
*: In the table, Mn and Mw/Mn indicate number-average molecular weight and molecular weight distribution, respectively, det-~rm;n~ by GPC. Fn (iso) and Fn (inn) indicate the number of isopropenyl groups and 2-methyl-1-propenyl groups per molecule, respectively. DCM indicates the content of methylene chloride in the wash water.
Experiments were conducted in the same manner as in Example 7 except that aluminum silicate was used in an amount of 0.1 g, 0.5 g and 2.6 g, respectively, instead of activated carbon to obtain isobutylene polymers. The results are shown in Table 9.
Table 9: Experiment with aluminum silicate as adsorbent Amount of aluminum silicate Mn Mw/Mn Fn ( iso ) Fn ( inn ) DCM
(g) 2.6 9,500 1.22 0 0 ND
0.5 9,400 1.20 0.09 0 ND
0.1 8,600 1.22 0.49 0.10 ND
In the same manner as in Example 7 except that no adsorbents were used, an isobutylene polymer was obtained.
The results are shown in Table 10.
Table 10: Comparative ~Yr~rir t free of adsorbent (1) Amount of adsorbent Mn Mw/Mn Fn (iso) Fn (inn) DCN
(g) 0 7,100 1.61 0.61 0.94 ND
COMPARATIVE EXAMPI,E 4 The polymer solution 2 (40 g) was poured into 100 g of methanol cooled with ice with vigorous stirring, and the solvent was removed by decantation. The resulting white precipitate was then re-dissolved in 30 m~ of n-hexane. The resulting organic phase was washed with ion-exchanged water three times. The material was then treated in the same manner as in Example 7 to obtain an isobutylene polymer. The results are shown in Table 11.
Table 11: Comparative ~YrPri - t free of adsorbent (2) Mn ~w/Mn Fn (iso) Fn (inn) 8,700 1.29 0 0 The cold methanol reprecipLtation method shown in Table 11 can produce a sample with least side reactions in laboratory isolation methods, but produces a mixed solvent which is difficult to purify. It has been found that such a polymer has a tertiary carbon-chlorine bond at the ends thereof. Therefore, the fact that Fn (iso) and Fn (inn) in Table 11 are each O indicates that no isomerization occurs at the ends of the polymer. In the method free of adsorbent shown in Table 10, the molecular weight distribution is increased with the progress of isomerization at the ends of the polymer, demonstrating that undesirable side reactions occur. The ~ r; ~on between Tables 8 and 9 shows that as the content of the adsorbent decreases, the results is close to that of the case using no adsorbent. Since methylene chloride had been removed bef ore washing with water in Tables 8 and 9, methylene chloride could not be detected in the wash water .
[ Industrial applicability]
As compared with the prior art, the process of the present invention has the following advantages:
1. Even if a halide such as methylene chloride is used as a solvent for the polymerization of isobutylene monomer, no waste water having such a halide dissolved therein is generated.
2. The washing step can be omitted from the standpoint of process mechanism.
3. The dehydrochlorination reaction at the ends of the polymer at the same time with the ligand exchange reaction makes it possible to easily obtain a telechelic isobutylene polymer having unsaturated groups without isolating a telechelic polymer terminated by chlorine group as an int~ te.
4. The dehydrochlorination reaction at the ends of the polymer under reduced pressure makes it possible to accelerate the polymerization reaction.
Claims (7)
1. A process for the isolation of an isobutylene polymer which comprises the cationic polymerization reaction in a non-aqueous system in the presence of a catalyst represented by the following general formula (I):
MXn (I) wherein M represents a metallic atom; n represents an integer of from 2 to 6; and the plurality of X may be the same or different and each represent a halogen atom or a monovalent hydrocarbon group, characterized in that the process comprises carrying out polymerization, carrying out the ligand exchange reaction of said catalyst, and then removing a component containing M in the general formula (I).
MXn (I) wherein M represents a metallic atom; n represents an integer of from 2 to 6; and the plurality of X may be the same or different and each represent a halogen atom or a monovalent hydrocarbon group, characterized in that the process comprises carrying out polymerization, carrying out the ligand exchange reaction of said catalyst, and then removing a component containing M in the general formula (I).
2. The process for the isolation of an isobutylene polymer according to Claim 1, wherein said ligand exchange reaction is effected with the addition of a compound represented by the following general formula (II):
Q(OR)m (II) wherein Q represents a metallic atom belonging to the group Ia, IIa, IIIb or IVn of the periodic table; m represents an integer of from 1 to 6; and R represents a hydrogen atom or a monovalent organic group, with the proviso that when m is 2 or more, the plurality of R may be the same or different, and simultaneously producing a telechelic isobutylene polymer.
Q(OR)m (II) wherein Q represents a metallic atom belonging to the group Ia, IIa, IIIb or IVn of the periodic table; m represents an integer of from 1 to 6; and R represents a hydrogen atom or a monovalent organic group, with the proviso that when m is 2 or more, the plurality of R may be the same or different, and simultaneously producing a telechelic isobutylene polymer.
3. A process for the isolation of an isobutylene polymer which comprises the cationic polymerization in a non-aqueous system in the presence of a catalyst represented by the foregoing general formula (I), characterized in that the process comprises producing a telechelic isobutylene polymer and simultaneously removing said catalyst with an adsorption material capable of adsorbing an acid.
4. A process for the isolation of an isobutylene polymer, which comprises carrying out cationic polymerization reaction in a non-aqueous system in the presence of a catalyst represented by the foregoing general formula (I);
adding a compound represented by the foregoing general formula (II) to effect the dehydrochlorination reaction at the ends of the polymer and the ligand exchange reaction of the catalyst so as to produce a telechelic isobutylene polymer having an unsaturated group; and removing a component containing M in the general formula (I).
adding a compound represented by the foregoing general formula (II) to effect the dehydrochlorination reaction at the ends of the polymer and the ligand exchange reaction of the catalyst so as to produce a telechelic isobutylene polymer having an unsaturated group; and removing a component containing M in the general formula (I).
5. The process for the isolation of an isobutylene polymer according to Claim 2 or 4, wherein said compound represented by the general formula (II) comprises at least one compound or a plurality of compounds selected from the group consisting of NaOH, ROH, LiOH, Ca(OH)2, NaHCO3, NaOCH3, KOCH3, LiOCH3, Ca(OCH3)2, Mg(OCH3)2, Al(OCH3)3, Ti(OCH3)4, NaOCH2CH3, KOCH2CH3, LiOCH2CH3, Ca(OCH2CH3)2, Mg(OCH2CH3)2, Al(OCH2CH3)3, Ti(OCH2CH3)4, NaOC(CH3)3, KOC(CH3)3, LiOC(CH3)3, NaOC(CH3)2CH2CH3, and Al[OCH(CH3)2]3.
6. The process for the isolation of an isobutylene polymer according to Claim 4 or 5, wherein said dehydrochlorination at the ends of the polymer is effected under reduced pressure, i.e., not higher than 700 mmHg.
7. The process for the isolation of an isobutylene polymer according to any one of Claims 1, 3, 5 and 6, wherein the following components (1) to (5) were mixed at a temperature of from -100°C to 0°C to prepare an isobutylene polymer:
(1) a cationically polymerizable monomer having isobutylene;
(2) a compound represented by the following general formula (III):
(III) wherein R1 represents an aromatic ring group or substituted or unsubstituted aliphatic hydrocarbon group; R2 and R3 may be the same or different and each represent a hydrogen atom or substituted or unsubstituted monovalent hydrocarbon group, with the proviso that when R1 is an aliphatic hydrocarbon group, at least one of R2 and R3 is not a hydrogen atom; X
represents a halogen atom, R4COO- group (in which R4 represents a hydrogen atom or a C1-5 alkyl group) or R5O-group (in which R5 represents a hydrogen atom or a C1-5 alkyl group); and w represents an integer of from 1 to 8 ;
(3) a catalyst represented by the foregoing general formula (I);
(4) an electron donor component having a donor number of from 15 to 50; and 5) a reaction solvent.
(1) a cationically polymerizable monomer having isobutylene;
(2) a compound represented by the following general formula (III):
(III) wherein R1 represents an aromatic ring group or substituted or unsubstituted aliphatic hydrocarbon group; R2 and R3 may be the same or different and each represent a hydrogen atom or substituted or unsubstituted monovalent hydrocarbon group, with the proviso that when R1 is an aliphatic hydrocarbon group, at least one of R2 and R3 is not a hydrogen atom; X
represents a halogen atom, R4COO- group (in which R4 represents a hydrogen atom or a C1-5 alkyl group) or R5O-group (in which R5 represents a hydrogen atom or a C1-5 alkyl group); and w represents an integer of from 1 to 8 ;
(3) a catalyst represented by the foregoing general formula (I);
(4) an electron donor component having a donor number of from 15 to 50; and 5) a reaction solvent.
Applications Claiming Priority (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6-072883 | 1994-03-18 | ||
| JP7288394 | 1994-03-18 | ||
| JP6-179669 | 1994-07-08 | ||
| JP6-179668 | 1994-07-08 | ||
| JP17966894 | 1994-07-08 | ||
| JP17966994 | 1994-07-08 | ||
| PCT/JP1995/000486 WO1995025754A1 (en) | 1994-03-18 | 1995-03-17 | Method of isolating isobutylene polymer |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2184999A1 true CA2184999A1 (en) | 1995-09-28 |
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ID=27301062
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002184999A Abandoned CA2184999A1 (en) | 1994-03-18 | 1995-03-17 | Method of isolating isobutylene polymer |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US5739267A (en) |
| EP (1) | EP0752429B1 (en) |
| CA (1) | CA2184999A1 (en) |
| DE (1) | DE69525615D1 (en) |
| WO (1) | WO1995025754A1 (en) |
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| US6956084B2 (en) * | 2001-10-04 | 2005-10-18 | Bridgestone Corporation | Nano-particle preparation and applications |
| US6838539B2 (en) | 2002-02-12 | 2005-01-04 | Bridgestone Corporation | Cureable silane functionalized sealant composition and manufacture of same |
| US7576155B2 (en) * | 2002-12-18 | 2009-08-18 | Bridgestone Corporation | Method for clay exfoliation, compositions therefore, and modified rubber containing same |
| US6875818B2 (en) | 2003-01-16 | 2005-04-05 | Bridgestone Corporation | Polymer nano-strings |
| US7205370B2 (en) * | 2004-01-12 | 2007-04-17 | Bridgestone Corporation | Polymeric nano-particles of flower-like structure and applications |
| US7718737B2 (en) * | 2004-03-02 | 2010-05-18 | Bridgestone Corporation | Rubber composition containing functionalized polymer nanoparticles |
| US8063142B2 (en) | 2004-03-02 | 2011-11-22 | Bridgestone Corporation | Method of making nano-particles of selected size distribution |
| US7112369B2 (en) * | 2004-03-02 | 2006-09-26 | Bridgestone Corporation | Nano-sized polymer-metal composites |
| US20050215693A1 (en) * | 2004-03-29 | 2005-09-29 | Xiaorong Wang | Clay modified rubber composition and a method for manufacturing same |
| US20050228074A1 (en) * | 2004-04-05 | 2005-10-13 | Bridgestone Corporation | Amphiphilic polymer micelles and use thereof |
| JP4714424B2 (en) * | 2004-04-20 | 2011-06-29 | Ｊｘ日鉱日石エネルギー株式会社 | Method for producing α-olefin polymer |
| US20050282956A1 (en) * | 2004-06-21 | 2005-12-22 | Xiaorong Wang | Reversible polymer/metal nano-composites and method for manufacturing same |
| US7998554B2 (en) * | 2004-07-06 | 2011-08-16 | Bridgestone Corporation | Hydrophobic surfaces with nanoparticles |
| US7572855B2 (en) | 2005-01-28 | 2009-08-11 | Bridgestone Corporation | Nano-composite and compositions manufactured thereof |
| US7579398B2 (en) * | 2005-02-02 | 2009-08-25 | Bridgestone Corporation | Nano-composite and compositions therefrom |
| US7659342B2 (en) * | 2005-02-03 | 2010-02-09 | Bridgestone Corporation | Polymer nano-particle with polar core and method for manufacturing same |
| US9061900B2 (en) * | 2005-12-16 | 2015-06-23 | Bridgestone Corporation | Combined use of liquid polymer and polymeric nanoparticles for rubber applications |
| US7538159B2 (en) | 2005-12-16 | 2009-05-26 | Bridgestone Corporation | Nanoparticles with controlled architecture and method thereof |
| US7884160B2 (en) | 2005-12-19 | 2011-02-08 | Bridgestone Corporation | Non-spherical nanoparticles made from living triblock polymer chains |
| US8288473B2 (en) * | 2005-12-19 | 2012-10-16 | Bridgestone Corporation | Disk-like nanoparticles |
| US7601772B2 (en) * | 2005-12-20 | 2009-10-13 | Bridgestone Corporation | Nano-composite and method thereof |
| US7560510B2 (en) | 2005-12-20 | 2009-07-14 | Bridgestone Corporation | Nano-sized inorganic metal particles, preparation thereof, and application thereof in improving rubber properties |
| US8697775B2 (en) * | 2005-12-20 | 2014-04-15 | Bridgestone Corporation | Vulcanizable nanoparticles having a core with a high glass transition temperature |
| US8877250B2 (en) * | 2005-12-20 | 2014-11-04 | Bridgestone Corporation | Hollow nano-particles and method thereof |
| US7935184B2 (en) | 2006-06-19 | 2011-05-03 | Bridgestone Corporation | Method of preparing imidazolium surfactants |
| WO2008014464A2 (en) | 2006-07-28 | 2008-01-31 | Bridgestone Corporation | Polymeric core-shell nanoparticles with interphase region |
| US7597959B2 (en) * | 2006-12-19 | 2009-10-06 | Bridgestone Corporation | Core-shell fluorescent nanoparticles |
| US7649049B2 (en) * | 2006-12-20 | 2010-01-19 | Bridgestone Corporation | Rubber composition containing a polymer nanoparticle |
| US7829624B2 (en) * | 2007-06-29 | 2010-11-09 | Bridgestone Corporation | One-pot synthesis of nanoparticles and liquid polymer for rubber applications |
| US8846819B2 (en) | 2008-12-31 | 2014-09-30 | Bridgestone Corporation | Core-first nanoparticle formation process, nanoparticle, and composition |
| US9062144B2 (en) * | 2009-04-03 | 2015-06-23 | Bridgestone Corporation | Hairy polymeric nanoparticles with first and second shell block polymer arms |
| US20110172364A1 (en) * | 2009-12-29 | 2011-07-14 | Chen Yaohong | Charged Nanoparticles And Method Of Controlling Charge |
| US9115222B2 (en) * | 2009-12-29 | 2015-08-25 | Bridgestone Corporation | Well defined, highly crosslinked nanoparticles and method for making same |
| KR101511708B1 (en) * | 2013-08-28 | 2015-04-13 | 대림산업 주식회사 | Apparatus and method for removing halogen generated during the polyisobutylene preparation process |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US2893981A (en) * | 1954-06-29 | 1959-07-07 | Exxon Research Engineering Co | Recovering olefin polymers |
| US2786828A (en) * | 1955-12-27 | 1957-03-26 | Exxon Research Engineering Co | Neutralization of friedel-crafts catalyst |
| US4197398A (en) * | 1974-12-04 | 1980-04-08 | Exxon Research & Engineering Co. | Process for neutralizing and deashing polypropylene |
| US4342849A (en) * | 1979-09-10 | 1982-08-03 | The University Of Akron | Novel telechelic polymers and processes for the preparation thereof |
| JPS59157035A (en) * | 1983-02-28 | 1984-09-06 | Kyowa Chem Ind Co Ltd | Removal of halogen component from organic compound containing halogen-containing catalyst |
| DE3336355A1 (en) * | 1983-10-06 | 1985-04-18 | Basf Ag, 6700 Ludwigshafen | METHOD FOR IMPROVING THE QUALITY OF POLYMERISATES OF ISOBUTEN |
| US4758631A (en) * | 1986-10-16 | 1988-07-19 | Dow Corning Corporation | Method of preparing allyl-terminated polyisobutylene |
| JPS63205305A (en) * | 1987-02-20 | 1988-08-24 | Kanegafuchi Chem Ind Co Ltd | Manufacture of isobutylene polymer with functional terminal |
| JPH0651752B2 (en) * | 1987-02-20 | 1994-07-06 | 鐘淵化学工業株式会社 | Process for producing isobutylene-based polymer having functional end |
| JP2618430B2 (en) * | 1988-04-11 | 1997-06-11 | 鐘淵化学工業株式会社 | Method for producing isobutylene-based polymer having isopropenyl group |
| JPH0759601B2 (en) * | 1989-05-08 | 1995-06-28 | 日本ゼオン株式会社 | Method for producing polymer |
| DE3942756A1 (en) * | 1989-12-23 | 1991-06-27 | Basf Ag | METHOD FOR CLEANING ISOBUTEN POLYMERS |
| IT1244724B (en) * | 1991-02-11 | 1994-08-08 | Enimont Anic Srl | PROCEDURE FOR THE PREPARATION OF COLORLESS HYDROCARBON RESINS AND ITS RESULTING PRODUCTS |
-
1995
- 1995-03-17 WO PCT/JP1995/000486 patent/WO1995025754A1/en active IP Right Grant
- 1995-03-17 EP EP95912465A patent/EP0752429B1/en not_active Expired - Lifetime
- 1995-03-17 CA CA002184999A patent/CA2184999A1/en not_active Abandoned
- 1995-03-17 US US08/704,607 patent/US5739267A/en not_active Expired - Fee Related
- 1995-03-17 DE DE69525615T patent/DE69525615D1/en not_active Expired - Lifetime
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| Publication number | Publication date |
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| WO1995025754A1 (en) | 1995-09-28 |
| US5739267A (en) | 1998-04-14 |
| EP0752429A1 (en) | 1997-01-08 |
| EP0752429A4 (en) | 1998-03-18 |
| EP0752429B1 (en) | 2002-02-27 |
| DE69525615D1 (en) | 2002-04-04 |
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